Fiber-Containing Carbohydrate Composition

ABSTRACT

A food product comprises an oligosaccharide composition that is digestion resistant or slowly digestible. The oligosaccharide composition can be produced by a process that comprises producing an aqueous composition that comprises at least one oligosaccharide and at least one monosaccharide by saccharification of starch, membrane filtering the aqueous composition to form a monosaccharide-rich stream and an oligosaccharide-rich stream, and recovering the oligosaccharide-rich stream. Alternatively, the oligosaccharide composition can be produced by a process that comprises heating an aqueous feed composition that comprises at least one monosaccharide or linear saccharide oligomer, and that has a solids concentration of at least about 70% by weight, to a temperature of at least about 40° C., and contacting the feed composition with at least one catalyst that accelerates the rate of cleavage or formation of glucosyl bonds for a time sufficient to cause formation of non-linear saccharide oligomers, wherein a product composition is produced that contains a higher concentration of non-linear saccharide oligomers than linear saccharide oligomers.

This application is a continuation-in-part of PCT/US2007/60961, filed onJan. 24, 2007, which claims priority from the following U.S.applications: Ser. No. 11/339,306, filed on Jan. 25, 2006, Ser. No.11/532,219, filed on Sep. 15, 2006, and Ser. No. 11/610,639, filed onDec. 14, 2006, all of which arc now pending, and all of which arcincorporated herein by reference.

BACKGROUND OF THE INVENTION

A variety of carbohydrates are used in food products, such as varioussugars and starches. Many of these carbohydrates are digested in thehuman stomach and small intestine. Dietary fiber in food products, incontrast, is generally not digested in the stomach or small intestine,but is potentially fermentable by microorganisms in the large intestine.

There is an interest in developing ingredients that are suitable for usein food products and that are either non-digestible or only digestibleto a limited extent, in order to enhance the dietary fiber content orreduce the caloric content of the food. These modifications have certainhealth benefits.

There is a need for edible materials which have a reduced content ofeasily digestible carbohydrates, and which can be used in place of, orin addition to, conventional carbohydrate products in foods.

SUMMARY OF THE INVENTION

One aspect of the invention is a process for making an oligosaccharidecomposition. The process comprises producing an aqueous composition thatcomprises at least one oligosaccharide and at least one monosaccharideby saccharification of starch; membrane filtering the aqueouscomposition to form a monosaccharide-rich stream and anoligosaccharide-rich stream; and recovering the oligosaccharide-richstream. In one embodiment of the invention, the oligosaccharide-richstream is slowly digestible by the human digestive system. “Slowlydigestible” as the term is used herein means that a substantial quantity(e.g., at least about 50% on a dry solids basis, and in some cases atleast about 75%, or at least about 90%) of the carbohydrates present inthe stream are either not digested at all in the human stomach and smallintestine, or arc only digested to a limited extent. In anotherembodiment of the invention, the oligosaccharide-rich stream isresistant to digestion by the human digestive system

Both in vitro and in vivo tests can be performed to estimate rate andextent of carbohydrate digestion in humans. The “Englyst Assay” is an invitro enzyme test that can be used to estimate the amounts of acarbohydrate ingredient that arc rapidly digestible, slowly digestibleor resistant to digestion (European Journal of Clinical Nutrition (1992)Volume 46 (Suppl. 2), pages S33-S50). Thus, any reference herein to “atleast about 50% by weight on a dry solids basis” of a material beingslowly digestible, or to a material being “primarily slowly digestible,”means that the sum of the percentages that are classified as slowlydigestible or as resistant by the Englyst assay totals at least about50%. Likewise, any reference herein to “at least about 50% by weight ona dry solids basis” of a material being digestion-resistant, or to amaterial being “primarily digestion-resistant,” means that thepercentage that is classified as resistant by the Englyst assay is atleast about 50%.

In one embodiment of the process, the aqueous composition that isproduced by saccharification of starch, followed by isomerization,comprises dextrose, fructose, and a mixture of oligosaccharides. Thisaqueous composition can be nanofiltered to separate it into themonosaccharide-rich permeate stream and the oligosaccharide-richretentate stream. The oligosaccharide-rich stream can comprise at leastabout 50% by weight oligosaccharides on a dry solids basis, or in somecases at least about 90%. In certain embodiments of the process, theoligosaccharide-rich stream will still comprise a minor amount ofdextrose and fructose. “A minor amount” is used herein to mean less than50% by weight on a dry solids basis.

The process, can, in some embodiments, also include one or more of thefollowing steps: (1) contacting the oligosaccharide-rich stream with anisomerization enzyme, such that at least some of the dextrose isconverted to fructose, thereby producing an isomerizedoligosaccharide-rich stream; (2) membrane filtering theoligosaccharide-rich stream to produce a second monosaccharide-richstream and a second oligosaccharide-rich stream that comprises more thanabout 90% by weight oligosaccharides on a dry solids basis as well as aminor amount of monosaccharides; (3) hydrogenating theoligosaccharide-rich stream to convert at least some of themonosaccharides therein to alcohols, thereby producing a hydrogenatedoligosaccharide-rich stream; (4) contacting the oligosaccharide-richstream with a glucosidasc enzyme to create a reversion product such thatat least some of any residual monosaccharides present in the stream arecovalently bonded to oligosaccharides or other monosaccharides; and (5)reducing the color of the oligosaccharide-rich stream by contacting itwith activated carbon.

Another aspect of the invention is a process for preparing saccharideoligomers. The saccharide oligomer composition produced by someembodiments of this process is primarily digestion resistant. In otherembodiment, the composition is primarily slowly digestible. The processuses an aqueous feed composition that comprises at least onemonosaccharide or linear saccharide oligomer, and that has a solidsconcentration of at least about 70% by weight. The feed composition isheated to a temperature of at least about 40° C., and is contacted withat least one catalyst that accelerates the rate of cleavage or formationof glucosyl bonds for a time sufficient to cause formation of non-linearsaccharide oligomers. A product composition is produced that contains ahigher concentration of non-linear saccharide oligomers than linearsaccharide oligomers.

In one embodiment of the process, the at least one catalyst is an enzymethat accelerates the rate of cleavage or formation of glucosyl bonds. Inanother embodiment of the process, the at least one catalyst is an acid.In some embodiments of the process, acid and enzyme can be used insequence, with the feed composition first being treated with enzyme andsubsequently with acid, or vice versa.

Another aspect of the invention is an edible carbohydrate composition(sometimes referred to herein as an oligosaccharide composition) thatcomprises a major amount of oligosaccharides on a dry solids basis, andthat is slowly digestible or resistant to digestion by the humandigestive system. This composition can be produced by any of theabove-described processes. “Major amount” is used herein to mean atleast 50% by weight on a dry solids basis.

In one embodiment, the edible carbohydrate composition is produced by aprocess in which the oligosaccharide rich stream has a solids contentnot less than 70.0 percent mass/mass (m/m), and a reducing sugar content(dextrose equivalent), expressed as D-glucose, that is not less than20.0 percent m/m calculated on a dry basis. This embodiment of thecomposition can be classified as corn syrup under food labelingregulations. In another embodiment, the oligosaccharide rich stream hasa solids content not less than 70.0 percent mass/mass (m/m), andreducing sugar content (dextrose equivalent), expressed as D-glucose,less than 20.0 percent m/m calculated on a dry basis. This embodimentcan be classified as maltodextrin under food labeling regulations.

Another aspect of the invention is an edible carbohydrate compositionthat comprises a major amount on a dry solids basis (i.e., greater than50% by weight on a dry solids basis) of linear and non-linear saccharideoligomers, wherein the concentration of non-linear saccharide oligomersis greater than the concentration of linear saccharide oligomers. Insome embodiments of the invention, the concentration of non-linearsaccharide oligomers in the composition is at least twice as high as theconcentration of linear saccharide oligomers.

Another embodiment is a carbohydrate composition that comprises linearand non-linear saccharide oligomers, wherein the composition containsabout 10-70% by weight fiber on a dry solids basis and has a dextroseequivalence of about 25-65. In some embodiments, the compositioncontains about 30-40% by weight fiber on a dry solids basis and has acaloric value of about 2.5-3.5 kcal/g.

The product of this embodiment can be prepared by a process thatcomprises: heating an aqueous feed composition that comprises at leastone monosaccharide or linear saccharide oligomer, and that has a solidsconcentration of at least about 70% by weight, to a temperature of atleast about 40° C.; and contacting the feed composition with at leastone catalyst that accelerates the rate of cleavage or formation ofglucosyl bonds for a time sufficient to cause formation of non-linearsaccharide oligomers, wherein a product composition is produced that (a)contains about 10-70% by weight fiber on a dry solids basis, and (b) hasa dextrose equivalence of about 25-65. The at least one catalyst can bean acid, such as citric acid, hydrochloric acid, sulfuric acid,phosphoric acid, or a combination thereof. In one particular embodiment,the acid can be residual acid that is present in the feed compositionfrom previous processing. In another embodiment, the at least onecatalyst can be an enzyme that accelerates the rate of cleavage orformation of glucosyl bonds. Alternatively, the composition can beprepared by blending corn syrup with a composition prepared by one ormore of the processes described herein.

Another aspect of the invention is a method of preparing a food product.The method comprises providing a food composition suitable forcombination with a carbohydrate material, and combining the foodcomposition with an edible carbohydrate composition that is slowlydigestible or digestion-resistant, as described above.

Another aspect of the invention is a food product that comprises anedible carbohydrate composition as described above. The food product canbe, for example, a bread, cake, cookie, cracker, extruded snack, soup,frozen dessert, fried food, pasta product, potato product, rice product,corn product, wheat product, dairy product, yogurt, confectionary, hardcandy, nutritional bar, breakfast cereal, or beverage.

In one embodiment of the invention, the food product is selected frombaked foods, breakfast cereal, anhydrous coatings (e.g., ice creamcompound coating, chocolate), dairy products, confections, jams andjellies, beverages, fillings, extruded and sheeted snacks, gelatindesserts, snack bars, cheese and cheese sauces, edible and water-solublefilms, soups, syrups, sauces, dressings, creamers, icings, frostings,glazes, pet food, tortillas, meat and fish, dried fruit, infant andtoddler food, and batters and breadings. The edible carbohydratecomposition, which is sometimes referred to herein as an oligosaccharidecomposition, can be present in the food product for one or morepurposes, such as a complete or partial replacement for sweetenersolids, or as a source of dietary fiber.

Another aspect of the invention is a method of controlling blood glucosein a mammal suffering from diabetes. The method comprises feeding to themammal a food product as described above in various embodiments.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is process flow diagram of one embodiment of the presentinvention.

FIG. 2 is a graph of the distribution of certain saccharides in threedextrose compositions used in Example 3.

FIG. 3 is a graph of the distribution of certain saccharides in thestarting materials used in Example 4.

FIG. 4 is a graph of the distribution of certain saccharides in theproducts prepared by enzyme treatment in Example 4.

FIG. 5 is a graph of the change over time in maltose and isomaltoseconcentrations when a composition was treated with enzyme in Example 4.

FIG. 6 is a graph of the change in maltose concentration and FIG. 7 is agraph of the change in isomaltose concentration when dextrose syrup wastreated with different concentrations of enzyme in Example 4.

FIG. 8 is a graph of the change over time in the concentrations ofcertain saccharides when a composition was treated with enzyme inExample 4.

FIG. 9 is a graph of the change over time in the concentrations ofcertain saccharides when a diluted composition was treated with enzymein Example 4.

FIG. 10 is a graph of the effect of temperature on the formation ofcertain saccharides as a result of enzyme treatment in Example 5.

FIG. 11 is a graph of the effect of temperature on the formation ofcertain saccharides as a result of another enzyme treatment in Example5.

FIG. 12 is a graph comparing the changes in saccharide distribution whena composition was treated by acid or by enzyme in Example 6.

FIG. 13 shows an analysis of a syrup treated with acid in Example 6.

FIG. 14 shows a chromatographic analysis of a syrup treated with acid inExample 6.

FIG. 15 shows the change in blood glucose concentration in dogs afterthey were fed either a composition of the present invention or amaltodextrin.

DESCRIPTION OF SPECIFIC EMBODIMENTS

One aspect of the present invention is a process for making a slowlydigestible or digestion-resistant carbohydrate composition (e.g.,saccharide oligomer composition) that is suitable for use in foods.

Both in vitro and in vivo tests can be performed to estimate the rateand extent of carbohydrate digestion in humans. The “Englyst Assay” isan in vitro enzyme test that can be used to estimate the amounts of acarbohydrate ingredient that are rapidly digestible, slowly digestibleor resistant to digestion (European Journal of Clinical Nutrition (1992)Volume 46 (Suppl. 2), pages S33-S50).

It should be understood that the term “food” is used in a broad senseherein to include a variety of substances that can be ingested byhumans, such as beverages and medicinal capsules or tablets.

The terms “oligosaccharides” and “saccharide oligomers” are used hereinto refer to saccharides comprising at least two saccharide units, forexample saccharides having a degree of polymerization (“DP”) of about2-30. For example, a disaccharide has a DP of 2.

In some embodiments of the invention, the aqueous feed compositionincludes at least one monosaccharide and at least one linear saccharideoligomer, and may contain several of each. In many cases,monosaccharides and oligosaccharides will make up at least about 70% byweight on a dry solids basis of the feed composition. It is generallyhelpful for the starting material to have as high a concentration ofmonosaccharides as possible, in order to maximize the yield of thedesired oligomers. A high solids concentration tends to drive theequilibrium from hydrolysis toward condensation (reversion), therebyproducing higher molecular weight products. Therefore the water contentof the starting material is preferably relatively low. For example, incertain embodiments, the feed composition comprises at least about 75%dry solids by weight. (“Dry solids” is sometimes abbreviated herein as“ds.”) In some cases, the feed composition comprises about 75-90% solidsby weight, which will generally give the appearance of a viscous syrupor damp powder at room temperature.

Examples of suitable starting materials include, but are not limited to,syrups made by hydrolysis of starch, such as dextrose greens syrup(i.e., recycle stream of mother liquor from dextrose monohydratecrystallization), other dextrose syrups, corn syrup, and solutions ofmaltodextrin.

If the feed composition comprises maltodextrin, the process optionallycan also include the steps of hydrolyzing the maltodextrin to form ahydrolyzed saccharide solution and concentrating the hydrolyzedsaccharide solution to at least about 70% dry solids to form the feedcomposition. The concentrating and the contacting of the feed with thecatalyst can occur simultaneously, or the concentrating can occur priorto contacting the feed composition with the catalyst.

The feed composition is contacted with the at least one catalyst for aperiod of time that can vary. In some cases, the contacting period willbe at least about five hours. In some embodiments of the invention, thefeed composition is contacted with the at least one catalyst for about15-100 hours. In other embodiments, shorter contacting times can be usedwith higher temperatures, in some cases even less than one hour.

In one embodiment of the invention, enzymatic reversion is used toproduce nonlinear oligosaccharides. The enzyme can be, for example, onethat accelerates the rate of cleavage of alpha 1-2, 1-3, 1-4, or 1-6glucosyl bonds to form dextrose residues. One suitable example is aglucoamylase enzyme composition, such as a commercial enzyme compositionthat is denominated as a glucoamylase. It should be understood that sucha composition can contain some quantity of enzymes other than pureglucoamylase, and it should not be assumed that it is in factglucoamylase itself that catalyzes the desired production of nonlinearoligosaccharides.

Therefore, the feed composition can be contacted with glucoamylase orany other enzyme that acts on dextrose polymers. The amount of enzymecan suitably be about 0.5-2.5% by volume of the feed composition. Insome embodiments of the process, the feed composition is maintained atabout 55-75° C. during the contacting with the enzyme, or in some casesabout 60-65° C. At this temperature, depending on the water content, thematerial will become a liquid, or a mixture of liquid and solid.Optionally, the reaction mixture can be mixed or agitated to distributethe enzyme. The reaction mixture is maintained at the desiredtemperature for the time necessary to achieve the desired degree ofreversion to non-linear oligomers. In some embodiments of the process,the feed composition is contacted with the enzyme for about 20-100 hoursprior to inactivation of the enzyme, or in some cases, for about 50-100hours prior to inactivation. Techniques for inactivating glucoamylaseare well known in the field. Alternatively, instead of inactivating theenzyme, it can be separated by membrane filtration and recycled.

The resulting composition has a high concentration of non-linearoligosaccharides, such as isomaltose. This product composition containsa higher concentration of non-linear saccharide oligomers than linearsaccharide oligomers. In some cases, the concentration of non-linearsaccharide oligomers in the final composition is at least twice as highas the concentration of linear saccharide oligomers.

Gastrointestinal enzymes readily recognize and digest carbohydrates inwhich the dextrose units are linked alpha (1->4) (“linear” linkages).Replacing these linkages with alternative linkages (alpha (1->3), alpha(1->6) (“non-linear” linkages) or beta linkages, for example) greatlyreduces the ability of gastrointestinal enzymes to digest thecarbohydrate. This will allow the carbohydrates to pass on into thesmall intestines largely unchanged.

In some cases, the product composition comprises a minor amount (i.e.,less than 50 wt % on a dry solids basis, and usually a much lowerconcentration) of residual monosaccharides. The process can include theadditional step of removing at least some of the residualmonosaccharides (and optionally other species as well) from the productcomposition by membrane filtration, chromatographic fractionation, ordigestion via fermentation. The separated monosaccharides can becombined with other process streams, for example for production ofdextrose or corn syrup. Alternatively, the separated monosaccharides canbe recycled into the feed composition.

Another embodiment of the invention is a process that involves acidreversion of monosaccharides. The starting material is the same asdescribed above with respect to the enzyme version of the process. Avariety of acids can be used, such as hydrochloric acid, sulfuric acid,phosphoric acid, or a combination thereof. In some embodiments of theprocess, acid is added to the feed composition in an amount sufficientto make the pH of the feed composition no greater than about 4, or insome cases, in an amount sufficient to make the pH of the feedcomposition about 1.0-2.5, or about 1.5-2.0. In some embodiments, thesolids concentration of the feed composition is about 70-90%, the amountof acid added to the feed is about 0.05%-0.25% (w/w) acid solids onsyrup dry solids, and the feed composition is maintained at atemperature of about 70-90° C. during the contacting with the acid. Asin the enzyme version of the process, the reaction conditions aremaintained for a time sufficient to produce the desired oligomers, whichin some embodiments of the process will be about 4-24 hours.

In one particular embodiment, the solids concentration of the feedcomposition is at least about 80% by weight, acid is added to the feedcomposition in an amount sufficient to make the pH of the compositionabout 1.8, and the feed composition is maintained at a temperature of atleast about 80° C. for about 4-24 hours after it is contacted with theacid.

In another particular embodiment, the solids concentration of the feedcomposition is about 90-100% by weight, and the feed composition ismaintained at a temperature of at least about 149° C. (300° F.) forabout 0.1-15 minutes after it is contacted with the acid. The acid usedto treat the feed can be a combination of phosphoric acid andhydrochloric acid (at the same concentrations discussed above). In oneparticular embodiment, the contacting of the feed composition with theacid takes place in a continuous pipe/flow through reactor.

By far the most plentiful glycosidic linkage in starch is the alpha-1,4linkage, and this is the linkage most commonly broken during acidhydrolysis of starch. But acid-catalyzed reversion (condensation) cantake place between any two hydroxyl groups, and, given the large varietyof combinations and geometries available, the probability of analpha-1,4 linkage being formed is relatively small. The human digestivesystem contains alpha amylases which readily digest the alpha-1,4linkages of starch and corn syrups. Replacing these linkages withlinkages unrecognized by enzymes in the digestive system will allow theproduct to pass through to the small intestines largely unchanged.

The saccharide distributions resulting from acid treatment are believedto be somewhat different than from enzyme treatment. It is believed thatthese acid-catalyzed condensation products will be less recognizable bythe enzymes in the human gut than enzyme-produced products, andtherefore less digestible.

The acid treatment progresses differently than enzyme treatment. Enzymesrapidly hydrolyze linear oligomers and slowly form non-linear oligomers,whereas with acid the reduction in linear oligomers and the increase innon-linear oligomers occur at comparable rates. Dextrose is formedrapidly by enzymatic hydrolysis of oligomers, and consumed slowly asnon-linear condensation products arc formed, whereas with acid dextroseconcentrations increase slowly.

Optionally, enzymatic or acid reversion can be followed byhydrogenation. The hydrogenated product should have lower caloriccontent than currently available hydrogenated starch hydrolysates. Inone embodiment, the hydrogenation can be used to decolorize the productcomposition without substantially changing its dextrose equivalence(DE).

In one version of the process, enzyme and acid can be used sequentially,in any order. For example, the at least one catalyst used in the firsttreatment can be enzyme, and the product composition can be subsequentlycontacted with an acid that accelerates the rate of cleavage orformation of glucosyl bonds. Alternatively, the at least one catalystused in the first treatment can be acid, and the product composition canbe subsequently contacted with an enzyme that accelerates the rate ofcleavage or formation of glucosyl bonds.

In an embodiment of the process in which acid treatment is used first,followed by an enzyme treatment, the acid can be phosphoric acid,hydrochloric acid, or a combination thereof. In this embodiment, afterbeing contacted with the enzyme, the composition can be contacted withan ion exchange resin. After being contacted with the ion exchangeresin, the concentration in the composition of saccharide oligomershaving a degree of polymerization of at least three can be at leastabout 50% by weight on a dry solids basis.

The product composition produced by the treatment with acid, enzyme, orboth, has an increased concentration on a dry solids basis of non-linearsaccharide oligomers. In some cases, the concentration of non-linearsaccharide oligomers having a degree of polymerization of at least three(DP3+) in the product composition is at least about 20%, at least about25%, at least about 30%, or at least about 50% by weight on a dry solidsbasis. In some embodiments, the concentration of non-linear saccharideoligomers in the product composition is at least twice as high as theconcentration of linear saccharide oligomers.

In one particular embodiment, the concentration of non-linear saccharideoligomers in the product composition is at least about 90% by weight ona dry solids basis, and the concentration of isomaltose is at leastabout 70% by weight on a dry solids basis.

The product composition will often contain some quantity (typically lessthan 50% by weight on a dry solids basis, and often much less) ofresidual monosaccharides. Optionally, at least some of the residualmonosaccharides (and other species) can be separated from the oligomers(for example by membrane filtration, chromatographic separation, ordigestion via fermentation) and the monosaccharide stream can berecycled into the process feed. In this way, simple sugar syrups can beconverted to high-value food additives.

The oligomer-rich syrup produced by the processes described herein canbe used in foods to increase dietary fiber. The syrup containsnaturally-occurring oligosaccharides that have both low viscosity andlow glycemic index. Many of these oligomers will comprise at least onenon-alpha-1,4 linkage. They should be highly fermentable in the largeintestine, which give them added health benefits as prebiotics. In someembodiments of the invention, at least about 50% by weight on a drysolids basis of the product composition is slowly digestible.

The beneficial effects of oligosaccharides as dietary fiber have beenwell documented. Sugar oligomers that resist digestion in the smallintestine but are fermentable in the large intestine have been shown tohave several beneficial effects, such as reducing cholesterol,attenuating blood dextrose, and maintaining gastrointestinal health.

In one embodiment, the product is a carbohydrate composition thatcomprises linear and non-linear saccharide oligomers, contains about10-70% by weight fiber on a dry solids basis, and has a dextroseequivalence (DE) of about 25-65. Fiber content can be measured by AOACmethod 2001.03.

In this embodiment, the product can have an intermediate fiber content(i.e., higher than conventional corn syrup but lower than some of thecompositions of the present invention that are described herein). Whenthe feed is derived from corn, the product can be referred to as cornsyrup fiber (CSF). In one embodiment, the CSF product contains about30-40% by weight fiber on a dry solids basis and has a caloric value ofabout 2.5-3.5 kcal/g. We estimate that a 35% fiber CSF will result in acaloric content of 3 kcal/g, which is intermediate between a high fiberresistant corn syrup at 2 kcal/g and typical digestible carbohydrate at4 kcal/g. This represents a caloric reduction of 25% compared totraditional sugars and starches.

In one embodiment, the process for making this product comprises (1)heating an aqueous feed composition that comprises at least onemonosaccharide or linear saccharide oligomer, and that has a solidsconcentration of at least about 70% by weight, to a temperature of atleast about 40° C., and (2) contacting the feed composition with atleast one catalyst that accelerates the rate of cleavage or formation ofglucosyl bonds for a time sufficient to cause formation of non-linearsaccharide oligomers, wherein a product composition is produced that (a)contains about 10-70% by weight fiber on a dry solids basis, and (b) hasa dextrose equivalence of about 25-65.

The catalyst can be acid (such as citric acid, hydrochloric acid,sulfuric acid, phosphoric acid, or a combination thereof), enzyme, or acombination of both acid and enzyme. The catalyst can be added duringthe process. Alternatively, in some situations there can be sufficientresidual catalyst (e.g., food grade acid) present in the feed as aresult of previous processing, so that no further catalyst needs to beadded. Thus, in one embodiment, the process to make CSF comprises asimple heating step, with optional addition of food grade acid. Thisprocess can be easily implemented and integrated into existing cornsyrup refinery operations.

We expect that the fiber fraction of this “direct reversion” CSF productwill be lower molecular weight, have less complicated branching and willbe more easily fermentable by colonic microbiota than the fiber fractionin the higher fiber resistant corn syrup (RCS). The DE of the CSFproduct can be targeted to match the DE of commercial corn syrupproducts. For example, CSF products with DE approximately equal to 26,35, 43 and 63 would be matches for Staley 200, Staley 300, Staley 1300and Sweetose 4300 traditional corn syrups, respectively.

Alternatively, the product can be prepared by blending conventional cornsyrup (having little or no fiber) with a resistant corn syrup (having afiber content of, for example, about 70% or greater). Syrups that arederived from grains other than corn can also be used.

The above-described product can be used as an ingredient in foodproducts, as explained in more detail in other parts of this patentapplication. This product can have one or more benefits. For example, itcan reduce the caloric content and increase the dietary fiber content ofcorn syrup, it can serve as a “drop in” replacement for traditional cornsyrup in foods, it can provide appropriate fiber loading in productsthat use high levels of corn syrup, and it can provide a more economicalapproach to fiber supplementation in food.

FIG. 1 shows one embodiment of a process which can make use of thereversion technique described above. The process can begin with astarch, for example a vegetable starch. Conventional corn starch is onesuitable example. The process will generally operate more efficiently ifthe beginning starch has a relatively high purity. In one embodiment,the high purity starch contains less than 0.5% protein on a dry solidsbasis. Although some of the following discussion focuses on corn, itshould be understood that the present invention is also applicable tostarches derived from other sources, such as potato and wheat, amongothers.

As shown in FIG. 1, the starch 10 can have acid 12 added to it and canthen be gelatinized 14 in a starch cooker, for example in a jet cookerin which starch granules are contacted with steam. In one version of theprocess, the starch slurry, adjusted to a pH target of 3.5 by additionof sulfuric acid, is rapidly mixed with steam in a jet cooker and heldat 149 to 152° C. (300 to 305° F.) for 4 minutes in a tail line. Thegelatinized starch 16 is hydrolyzed 18 by exposure to acid at hightemperature during jet cooking. The hydrolysis reduces the molecularweight of the starch and generates an increased percentage ofmonosaccharides and oligosaccharides in the composition. (As mentionedabove, the term “oligosaccharides” is used herein to refer tosaccharides comprising at least two saccharide units, for examplesaccharides having a degree of polymerization (DP) of about 2-30.) Aneutralizing agent 20, such as sodium carbonate, can be added to stopthe acid hydrolysis, and then the composition can be furtherdepolymerized 24 by contacting it with a hydrolytic enzyme 22. Suitableenzymes include alpha amylases such as Termamyl, which is available fromNovozymes. This enzymatic hydrolysis further increases the percentage ofmonosaccharides and oligosaccharides present in the composition. Theoverall result of the hydrolysis by acid and enzyme treatment is tosaccharify the starch. The saccharified composition can be isomerized tochange the monosaccharide profile, for example to increase theconcentration of fructose.

The saccharified composition 26 can then be purified, for example bychromatographic fractionation 28. In one embodiment that employs asequential simulated moving bed (SSMB) chromatography procedure, asolution of mixed saccharides is pumped through a column filled withresin beads. Depending on the chemical nature of the resin, some of thesaccharides interact with the resin more strongly leading to a retardedflow through the resin compared to saccharides that interact with theresin more weakly. This fractionation can produce one stream 30 that hasa high content of monosaccharides, such as dextrose and fructose. Highfructose corn syrup is an example of such a stream. The fractionationalso produces a raffinate stream 32 (i.e., faster moving componentsthrough the resin bed) that has a relatively high concentration ofoligosaccharides (e.g., about 5-15% oligosaccharides on a dry solidsbasis (d.s.b.)) and also contains a smaller concentration ofmonosaccharides such as dextrose and fructose. Although the term“stream” is used herein to describe certain parts of the process, itshould be understood that the process of the present invention is notlimited to continuous operation. The process can also be performed inbatch or semi-batch mode.

The raffinate 32 can be further fractionated by membrane filtration 34,for example by nanofiltration, optionally with diafiltration. Forexample, these filtration steps can be performed using a Desal DK spiralwound nanofiltration cartridge at about 500 psi of pressure and at 40-60degrees centigrade temperature. The fractionation described in step 34could also be accomplished by sequential simulated moving bedchromatography (SSMB). The membrane filtration produces a permeate 36(i.e., components that pass through the membrane) which comprisesprimarily monosaccharides, and a retentate 38 (i.e., components rejectedby the membrane) which comprises primarily oligosaccharides.(“Primarily” as used herein means that the composition contains more ofthe listed component than of any other component on a dry solids basis.)The permeate 36 can be combined with the monomer stream 30 (e.g., highfructose corn syrup). The permeate is a monosaccharide-rich stream andthe retentate is an oligosaccharide-rich stream. In other words, thenanofiltration concentrates the oligosaccharides in the retentate andthe monosaccharides in the permeate, relative to the nanofiltrationfeed.

The retentate 38, which can be described as an oligosaccharide syrup 40,can have a sufficiently high content of oligosaccharides that are slowlydigestible (e.g., at least about 50% by weight d.s.b., or in some casesat least about 90%) so that it can be dried or simply evaporated to aconcentrated syrup and used as an ingredient in foods. However, in manycases, it will be useful to further process and purify this composition.Such purification can include one or more of the following steps.(Although FIG. 1 shows four such purification steps 42, 44, 46, and 48as alternatives, it should be understood that two or more of these stepscould be used in the process.)

The oligomers syrup 40 can be subjected to another fractionation 42,such as a membrane filtration, for example a second nanofiltration, inorder to remove at least some of the residual monosaccharides, such asfructose and dextrose. Suitable nanofiltration conditions and equipmentare as described above. This nanofiltration produces a permeate, whichis a second monosaccharide-rich stream, which can be combined with themonomer stream 30. Alternatively, the further fractionation 42 could bedone by chromatographic separation, for example, by simulated mixed-bedchromatography.

The syrup 41 can be isomerized 44 by contacting it with an enzyme suchas dextrose isomerase. This will convert at least some of the residualdextrose present into fructose, which may be more valuable in certainsituations.

As mentioned above, the syrup can be treated with an enzyme or acid tocause reversion or repolymerization 46, in which at least some of themonosaccharides that are still present are covalently bonded to othermonosaccharides or to oligosaccharides, thereby reducing the residualmonomer content of the syrup even further. Suitable enzymes for use inthis step include glucosidases, such as amylase, glucoamylase,transglucosidase, and pullulanase. Cellulase enzymes may producevaluable reversion products for some applications.

The syrup can be hydrogenated 48 to convert at least some of anyresidual monosaccharides to the corresponding alcohols (e.g., to convertdextrose to sorbitol). When hydrogenation is included in the process, itwill typically (but not necessarily) be the final purification step.

The purified oligomer syrup 49 produced by one or more of the abovepurification steps can then be decolorized 50. Decolorization can bedone by treatment with activated carbon followed by microfiltration, forexample. In continuous flow systems, syrup streams can be pumped throughcolumns filled with granular activated carbon to achieve decolorization.The decolorized oligomer syrup can then be evaporated 52, for example toabout greater than about 70% dry solids (d.s.), giving a product thatcomprises a high content of oligosaccharides (e.g., greater than 90% bywt d.s.b., and in some instances greater than 95%), and acorrespondingly low monosaccharide content. The product comprises aplurality of saccharides which are slowly or incompletely digested byhumans, if not totally indigestible. These sugars can includeisomaltosc, panose and branched oligomers having a degree ofpolymerization of four or greater.

The process conditions can be modified to recover the majority of themaltose in the feed either in the monomer-rich streams (30, 36) or inthe oligomer product stream. For example, a nanofiltration membrane witha slightly more open pore size, such as Desal DL, operating at less than500 psi pressure can be used to increase the amount of maltose inmonomer-rich streams.

The product is suitable as an ingredient for foods, and is slowlydigestible or resistant to digestion by the human digestive system. Asmentioned above, some components of the product can be substantiallyentirely indigestible in the human stomach and small intestine.Depending on the starch source used, the product can be classified insome embodiments as corn syrup or wheat syrup, as those terms are usedin food labeling. In cases where more open pore sizes are used innanofiltration, a higher molecular weight oligomer syrup productclassified as a maltodextrin can be obtained.

The oligosaccharide-containing syrup produced by the process can beadded to foods as replacement or supplement for conventionalcarbohydrates. Thus, another aspect of the invention is a food productthat comprises a carbohydrate composition that comprises a major amounton a dry solids basis of linear and non-linear saccharide oligomers,wherein the concentration of non-linear saccharide oligomers is greaterthan the concentration of linear saccharide oligomers. Specific examplesof foods in which the syrup can be used include processed foods such asbread, cakes, cookies, crackers, extruded snacks, soups, frozendesserts, fried foods, pasta products, potato products, rice products,corn products, wheat products, dairy products, yogurts, confectionaries,hard candies, nutritional bars, breakfast cereals, and beverages. A foodproduct containing the oligosaccharide syrup will have a lower glycemicresponse, lower glycemic index, and lower glycemic load than a similarfood product in which a conventional carbohydrate, such as corn starch,is used. Further, because at least some of the oligosaccharides areeither only digested to a very limited extent or are not digested at allin the human stomach or small intestine, the caloric content of the foodproduct is reduced. The syrup is also a source of soluble dietary fiber.

The digestion-resistant oligomer syrup described above can be used as aningredient in food products as a syrup, or it can first be concentratedto form syrup solids. In either form, it can be used in a number ofways. As mentioned above, this syrup can be derived from various starchsources, such as corn. In some instances in this patent, the phrase“digestion-resistant corn syrup” or “resistant corn syrup” (sometimesabbreviated as “RCS”) will be used, but it should be understood that theinvention is not limited to syrups or syrup solids that are derived fromcorn.

The digestion-resistant oligomer syrup can be added to food products asa source of soluble fiber. It can increase the fiber content of foodproducts without having a negative impact on flavor, mouth feel, ortexture.

The functionality of the digestion-resistant oligomer syrup is similarto corn syrup and sugar, which makes it suitable for complete or partialreplacement of various nutritive sweeteners in food products. Forexample, the resistant syrup can be used for total or partialreplacement of sucrose, high fructose corn syrup (HFCS), fructose,dextrose, regular corn syrup, or corn syrup solids in food products. Asone particular example, the digestion-resistant syrup ordigestion-resistant syrup solids can be used to replace other sweetenersolids on a 1:1 basis, up to a complete replacement of the sugar solids.At high sweetener solids replacement levels, the sweetness of the foodproduct could be decreased, but mouth feel and flavor release wouldremain substantially the same, while sugar and calorie content would bereduced. Also, the digestion-resistant syrup could be used as a bulkingagent, replacing fat, flour, or other ingredients in a food formula.Alternatively, the digestion-resistant syrup can be used in foodproducts in combination with sweeteners such as sucrose, HFCS, orfructose, resulting in no change in overall sweetness of the foodproduct. As another example, the digestion-resistant syrup can be usedin food products in combination with sucralose or other high intensitysweeteners, which allows sweetener replacement with no change insweetness or mouth feel of the food product.

The digestion-resistant oligomer syrup can be used in food products incombination with resistant starch, polydextrose, or other fiber sources,to boost the fiber content of the food product, enhance physiologicalbenefit from consumption of the product, reduce the caloric content,and/or enhance the nutritional profile of the product.

The digestion-resistant oligomer syrup can be used in food products incombination with bulking agents, such as sugar alcohols ormaltodextrins, to reduce caloric content and/or to enhance nutritionalprofile of the product. The syrup can also be used as a partialreplacement for fat in food products.

The digestion-resistant oligomer syrup can be used in food products as atenderizer or texturizer, to increase crispness or snap, to improve eyeappeal, and/or to improve the rheology of dough, batter, or other foodcompositions. The syrup can also be used in food products as ahumectant, to increase product shelf life, and/or to produce a softer,moister texture. It can also be used in food products to reduce wateractivity or to immobilize and manage water. Additional uses of the syrupinclude: to replace egg wash and/or to enhance the surface sheen of afood product, to alter flour starch gelatinization temperature, tomodify the texture of the product, and to enhance browning of theproduct.

At least in some embodiments of the invention, the digestion-resistantoligomer syrup has one or more of the following advantages: highsolubility, which makes it relatively easy to incorporate into foodcompositions, such as batters and doughs; stability under elevatedtemperatures and/or acidic pH (some other soluble fibers, such asinulin, are not as stable), lower sweetness, clean flavor, and clearcolor. The properties of the syrup allow food products in which it isused to have a clean, label. In some embodiments of the invention, thedigestion-resistant oligomer syrup contains about 2 calories per gram(d.s.b.), which can reduce the total calorie content of a food product.

The digestion-resistant oligomer syrup of the present invention can beused in a variety of types of food products. One type of food product inwhich the syrup can be very useful is bakery products (i.e., bakedfoods), such as cakes, brownies, cookies, cookie crisps, muffins,breads, and sweet doughs. Conventional bakery products can be relativelyhigh in sugar and high in total carbohydrates. The use of thedigestion-resistant syrup as an ingredient in bakery products can helplower the sugar and carbohydrate levels, as well as reduce the totalcalories, while increasing the fiber content of the bakery product.

There are two main categories of bakery products: yeast-raised andchemically-leavened. In yeast-raised products, like donuts, sweetdoughs, and breads, the digestion-resistant oligomer syrup can be usedto replace sugars, but a small amount of sugar may still be desired dueto the need for a fermentation substrate for the yeast or for crustbrowning Digestion-resistant oligomer syrup solids (e.g.,digestion-resistant corn syrup solids) could be added in a mannersimilar to nutritive dry sweeteners, with other dry ingredients, andwould require no special handling. The resistant corn syrup can be addedwith other liquids as a direct replacement for syrups or liquidsweeteners. The dough would then be processed under conditions commonlyused in the baking industry including being mixed, fermented, divided,formed or extruded into loaves or shapes, proofed, and baked or fried.The product can be baked or fried using conditions similar totraditional products. Breads arc commonly baked at temperatures rangingfrom 420° F. to 520° F. for 20 to 23 minutes and doughnuts can be friedat temperatures ranging from 400-415° F., although other temperaturesand times could also be used. High intensity sweeteners can be added todoughs as required to obtain optimum sweetness and flavor profile.

Chemically leavened products typically have more sugar and may containhave a higher level of resistant corn syrup/solids. A finished cookiecan contain 30% sugar, which could be replaced, entirely or partially,with resistant corn syrup/solids. These products could have a pH of4-9.5, for example. The moisture content can be between 2-40%, forexample.

The resistant corn syrup/solids is readily incorporated and may be addedto the fat at the beginning of mixing during a creaming step or in a anymethod similar to the syrup or dry sweetener that it is being used toreplace. The product would be mixed and then formed, for example bybeing sheeted, rotary cut, wire cut, or through another forming process.The products would then be baked under typical baking conditions, forexample at 200-450° F.

The resistant corn syrup/solids can also be used to form sugar glassesin the amorphous state, to adhere particles to baked goods, and/or usedto form a film or coating which enhances the appearance of a baked good.Resistant corn syrup solids, like other amorphous sugars, form glasseswith heating and subsequent cooling to a temperature below their glasstransition temperature.

Another type of food product in which the syrup can be used is breakfastcereal. For example, resistant corn syrup in accordance with the presentinvention could be used to replace all or part of the sugar in extrudedcereal pieces and/or in the coating on the outside of those pieces. Thecoating is typically 30-60% of the total weight of the finished cerealpiece. The syrup can be applied in a spray or drizzled on, for example.The formula for the coating can be as simple as a 75% solution ofresistant corn syrup. The resistant corn syrup could also be blendedwith sugar at various percentages, or with other sweeteners or polyols.The extra moisture could then be evaporated in a low heat oven. In anextruded piece, the resistant corn syrup solids could be added directlywith the dry ingredients, or the syrup form could be metered into theextruder with water or separately. A small amount of water could beadded in the extruder, and then it could pass through various zonesranging from 100° F. to 300° F. Optionally, other sources of fiber suchas resistant starch can be used in the extruded piece. Using theresistant corn syrup would create a different texture than other fibersources. Using it alone or in combination with other fibers may alterthe texture to create product diversity.

Another type of food product in which the syrup can be used is dairyproducts. Examples of dairy products in which it can be used includeyogurt, yogurt drinks, milk drinks, flavored milks, smoothies, icecream, shakes, cottage cheese, cottage cheese dressing, and dairydesserts, such as quarg and the whipped mousse-type products. This wouldinclude dairy products that arc intended to be consumed directly (e.g.,packaged smoothies) as well as those that are intended to be blendedwith other ingredients (e.g., blended smoothie). It can be used inpasteurized dairy products, such as ones that are pasteurized at atemperature from 160° F. to 285° F. Complete replacement of sugars in adairy product is possible (which would be up to 24% of the totalformula). The resistant corn syrup is generally stable at acid pH's (thepH range of dairy beverages typically would be 2-8).

Another type of food product in which the syrup can be used isconfections. Examples of confections in which it can be used includehard candies, fondants, nougats and marshmallows, gelatin jelly candiesor gummies, jellies, chocolate, licorice, chewing gum, caramels andtoffees, chews, mints, tableted confections, and fruit snacks. In fruitsnacks, the resistant corn syrup could be used in combination with fruitjuice. The fruit juice would provide the majority of the sweetness, andthe resistant corn syrup would reduce the total sugar content and addfiber. The syrup can be added to the initial candy slurry and heated tothe finished solids content. The slurry could be heated from 200-305° F.to achieve the finished solids content. Acid could be added before orafter heating to give a finished pH of 2-7. The resistant corn syrupcould be used as a replacement for 0-100% of the sugar and 1-100% of thecorn syrup or other sweeteners present.

Another type of food product in which the syrup can be used is jams andjellies. Jams and jellies are made from fruit. A jam contains fruitpieces, while jelly is made from fruit juice. The resistant corn syrupcan be used in place of sugar or other sweeteners as follows: Weighfruit and juice into a tank. Premix sugar, resistant corn syrup andpectin. Add the dry composition to the liquid and cook to a temperatureof 214-220° F. Hot fill into jars and retort for 5-30 minutes.

Another type of food product in which the syrup can be used isbeverages. Examples of beverages in which it can be used includecarbonated beverages, fruit juices, concentrated juice mixes (e.g.,margarita mix), clear waters, and beverage dry mixes. The use of theresistant corn syrup of the present invention would in many casesovercome the clarity problems that result when other types of fiber areadded to beverages. A complete replacement of sugars is possible (whichcould be, for example, up to 12% of the total formula). Because of thestability of the syrup at acid pHs, it could be used in beverages havingpH ranging from 2-7, for example. The resistant corn syrup could be usedin cold processed beverages and in pasteurized beverages.

Another type of food product in which the syrup can be used is highsolids fillings. Examples of high solids fillings in which it can beused include fillings in snack bars, toaster pastries, donuts, andcookies. The high solids filling could be an acid/fruit filling or asavory filling, for example. It could be added to products that would beconsumed as is, or products that would undergo further processing, by afood processor (additional baking) or by a consumer (bake stablefilling). In some embodiments of the invention, the high solids fillingswould have a solids concentration between 67-90%. The solids could beentirely replaced with resistant corn syrup, or it could be used for apartial replacement of the other sweetener solids present (e.g.,replacement of current solids from 5-100%). Typically fruit fillingswould have a pH of 2-6, while savory fillings would be between 4-8 pH.Fillings could be prepared cold, or heated at up to 250° F. to evaporateto the desired finished solids content.

Another type of food product in which the syrup can be used is extrudedand sheeted snacks. Examples of extruded and sheeted snacks in which itcan be used include puffed snacks, crackers, tortilla chips, and cornchips. In preparing an extruded piece, the resistant corn syrup/solidswould be added directly with the dry products. A small amount of waterwould be added in the extruder, and then it would pass through variouszones ranging from 100° F. to 300° F. This dry resistant cornsyrup/solids could be added at levels from 0-50% of the dry productsmixture. The liquid resistant corn syrup could also be added at one ofthe liquid ports along the extruder. The product would come out ateither a low moisture content (5%) and then baked to remove the excessmoisture, or at a slightly higher moisture content (10%) and then friedto remove moisture and cook out the product. Baking could be attemperatures up to 500° F. for 20 minutes. Baking would more typicallybe at 350° F. for 10 minutes. Frying would typically be at 350° F. for2-5 minutes. In a sheeted snack, the resistant corn syrup solids couldbe used as a partial replacement of the other dry ingredients (e.g.,flour). It could be from 0-50% of the dry weight. The product would bedry mixed, and then water added to form cohesive dough. The product mixcould have a pH from 5 to 8. The dough would then be sheeted and cut andthen baked or fried. Baking could be at temperatures up to 500° F. for20 minutes. Frying would typically be at 350° F. for 2-5 minutes.Another potential benefit from the use of the resistant corn syrup is areduction of the fat content of fried snacks by as much as 15% when itis added as an internal ingredient or as a coating on the outside of afried food.

Another type of food product in which the syrup can be used is gelatindesserts. The ingredients for gelatin desserts arc often sold as a drymix with gelatin as a gelling agent. The sugar solids could be replacedpartially or entirely with resistant corn syrup solids in the dry mix.The dry mix can then be mixed with water and heated to 212° F. todissolve the gelatin and then more water and/or fruit can be added tocomplete the gelatin dessert. The gelatin is then allowed to cool andset. Gelatin can also be sold in shelf stable packs. In that case thestabilizer is usually carrageenan-based. As stated above, resistant cornsyrup can replace up to 100% of the other sweetener solids. The dryingredients are mixed into the liquids and then pasteurized and put intocups and allowed to cool and set. The cups usually have a foil top.

Another type of food product in which the syrup can be used is snackbars. Examples of snack bars in which it can be used include breakfastand meal replacement bars, nutrition bars, granola bars, protein bars,and cereal bars. It could be used in any part of the snack bars, such asin the high solids filling, the binding syrup or the particulateportion. A complete or partial replacement of sugar in the binding syrupis possible with the resistant corn syrup. The binding syrup istypically from 50-90% solids and applied at a ratio ranging from 10%binding syrup to 90% particulates, to 70% binding syrup to 30%particulates. The binding syrup is made by heating a solution ofsweeteners, bulking agents and other binders (like starch) to 160-230°F. (depending on the finished solids needed in the syrup). The syrup isthen mixed with the particulates to coat the particulates, providing acoating throughout the matrix. The resistant corn syrup could also beused in the particulates themselves. This could be an extruded piece,directly expanded or gun puffed. It could be used in combination withanother grain ingredient, corn meal, rice flour or other similaringredient.

Another type of food product in which the syrup can be used is cheese,cheese sauces, and other cheese products. Examples of cheese, cheesesauces, and other cheese products in which it can be used include lowermilk solids cheese, lower fat cheese, and calorie reduced cheese. Inblock cheese, it can help to improve the melting characteristics, or todecrease the effect of the melt limitation added by other ingredientssuch as starch. It could also be used in cheese sauces, for example as abulking agent, to replace fat, milk solids, or other typical bulkingagents.

Another type of food product in which the syrup/solids can be used isfilms that are edible and/or water soluble. Examples of films in whichit can be used include films that are used to enclose dry mixes for avariety of foods and beverages that arc intended to be dissolved inwater, or films that are used to deliver color or flavors such as aspice film that is added to a food after cooking while still hot. Otherfilm applications include, but are not limited to, fruit and vegetableleathers, and other flexible films.

Another type of food product in which the syrup can be used is soups,syrups, sauces, and dressings. A typical dressing could be from 0-50%oil, with a pH range of 2-7. It could be cold processed or heatprocessed. It would be mixed, and then stabilizer would be added. Theresistant corn syrup could easily be added in liquid or dry form withthe other ingredients as needed. The dressing composition may need to beheated to activate the stabilizer. Typical heating conditions would befrom 170-200° F. for 1-30 minutes. After cooling, the oil is added tomake a pre-emulsion. The product is then emulsified using a homogenizer,colloid mill, or other high shear process.

Sauces can have from 0-10% oil and from 10-50% total solids, and canhave a pH from 2-8. Sauces can be cold processed or heat processed. Theingredients are mixed and then heat processed. The resistant corn syrupcould easily be added in liquid or dry form with the other ingredientsas needed. Typical heating would be from 170-200° F. for 1-30 minutes.

Soups are more typically 20-50% solids and in a more neutral pH range(4-8). They can be a dry mix, to which the dry resistant corn syrupsolids could be added, or a liquid soup which is canned and thenretorted. In soups, resistant corn syrup could be used up to 50% solids,though a more typical usage would be to deliver 5 g of fiber/serving.

Syrups can incorporate the resistant corn syrup as up to a 100%replacement of the sugar solids. Typically that would be 12-20% of thesyrup on an as-is basis. The resistant corn syrup would be added withthe water and then pasteurized and hot filled to make the product safeand shelf stable (typically 185° F. for one minute pasteurization).

Another type of food product in which the syrup can be used is coffeecreamers. Examples of coffee creamers in which it can be used includeboth liquid and dry creamers. A dry blended coffee creamer can beblended with commercial creamer powders of the following fat types:soybean, coconut, palm, sunflower, or canola oil, or butterfat. Thesefats can be non-hydrogenated or hydrogenated. The resistant corn syrupsolids can be added as a fiber source, optionally together withfructo-oligosaccharides, polydextrose, inulin, maltodextrin, resistantstarch, sucrose, and/or conventional corn syrup solids. The compositioncan also contain high intensity sweeteners, such as sucralose,acesulfame potassium, aspartame, or combinations thereof. Theseingredients can be dry blended to produce the desired composition.

A spray dried creamer powder is a combination of fat, protein andcarbohydrates, emulsifiers, emulsifying salts, sweeteners, andanti-caking agents. The fat source can be one or more of soybean,coconut, palm, sunflower, or canola oil, or butterfat. The protein canbe sodium or calcium caseinates, milk proteins, whey proteins, wheatproteins, or soy proteins. The carbohydrate can be the resistant cornsyrup alone or in combination with fructo-oligosaccharides,polydextrose, inulin, resistant starch, maltodextrin, sucrose, or cornsyrup. The emulsifiers can be mono- and diglycerides, acetylated mono-and diglycerides, or propylene glycol monoesters. The salts can betrisodium citrate, monosodium phosphate, di sodium phosphate, trisodiumphosphate, tetrasodium pyrophosphate, monopotassium phosphate, and/ordipotassium phosphate. The composition can also contain high intensitysweeteners, such as sucralose, acesulfame potassium, aspartame, orcombinations thereof. Suitable anti-caking agents include sodiumsilicoaluminates or silica dioxides. The products are combined inslurry, optionally homogenized, and spray dried in either a granular oragglomerated form.

Liquid coffee creamers are simply a homogenized and pasteurized emulsionof fat (either dairy fat or hydrogenated vegetable oil), some milksolids or caseinates, corn syrup, and vanilla or other flavors, as wellas a stabilizing blend. The product is usually pasteurized via HTST(high temperature short time) at 185° F. for 30 seconds, or UHT(ultra-high temperature), at 285° F. for 4 seconds, and homogenized in atwo stage homogenizer at 500-3000 psi first stage, and 200-1000 psisecond stage. The coffee creamer is usually stabilized so that it doesnot break down when added to the coffee.

Another type of food product in which the syrup can be used is foodcoatings such as icings, frostings, and glazes. In icings and frostings,the resistant corn syrup can be used as a sweetener replacement(complete or partial) to lower caloric content and increase fibercontent. Glazes arc typically about 70-90% sugar, with most of the restbeing water, and the resistant corn syrup can be used to entirely orpartially replace the sugar. Frosting typically contains about 2-40% ofa liquid/solid fat combination, about 20-75% sweetener solids, color,flavor, and water. The resistant corn syrup can be used to replace allor part of the sweetener solids, or as a bulking agent in lower fatsystems.

Another type of food product in which the syrup can be used is pet food,such as dry or moist dog food. Pet foods arc made in a variety of ways,such as extrusion, forming, and formulating as gravies. The resistantcorn syrup could be used at levels of 0-50% in each of these types.

Another type of food product in which the syrup can be used istortillas, which usually contain flour and/or corn meal, fat, water,salt, and fumaric acid. The resistant corn syrup could be used toreplace flour or fat. The ingredients are mixed and then sheeted orstamped and cooked. This addition could be used to add fiber or extendthe shelf life.

Another type of food product in which the syrup can be used is fish andmeat. Conventional corn syrup is already used in some meats, so theresistant corn syrup can be used as a partial or complete substitute.For example, the resistant corn syrup could be added to brine before itis vacuum tumbled or injected into the meat. It could be added with saltand phosphates, and optionally with water binding ingredients such asstarch, carrageenan, or soy proteins. This would be used to add fiber, atypical level would be 5 g/serving which would allow a claim ofexcellent source of fiber.

Another type of food product in which the syrup can be used is dried(infused) fruit. Many kinds of dried fruit are only stable and palatableif they are infused with sugar. The resistant corn syrup can besubstituted for all or part of the sugar. For example, the resistantcorn syrup could be added to the brine used to infuse the fruit beforedrying. Stabilizing agents such as sulfates can be used in this brine aswell.

Another type of food product in which the syrup can be used is infantand toddler food. The resistant corn syrup could be used as areplacement or a supplement to one or more conventional ingredients forsuch food. Because of its mild flavor and clear color, it could be addedto a variety of baby foods to reduce sugar and increase fiber content.

Another type of food product in which the syrup can be used is battersand breadings, such as the batters and breadings for meat. This could bedone by replacing all or part of the dry components of the batter and/orbreading (e.g., flour type ingredients) with the resistant corn syrup,or to use in combination with addition to the meat muscle or fried fooditself. This could be used as a bulking agent, for fiber addition, or toreduce fat in the fried food.

The process described herein takes advantage of a fraction of thesaccharide syrup (e.g., stream 26 in FIG. 1) that is resistant tosaccharification. By separating this material as a purified product, itcan be employed for its own useful properties, rather than being anundesirable by-product in syrups that are primarily monosaccharides,such as high fructose corn syrup. Removal of a greater percentage of theoligosaccharides from the high fructose corn syrup allows that productto be made purer (i.e., with a higher concentration of dextrose andfructose) and thus more valuable.

Food products of the present invention can also be used to help controlthe blood glucose concentration in mammals, such as humans, that sufferfrom diabetes. When the food product is consumed by the mammal, theslowly digestible and/or digestion resistant components in the foodproduct can cause a more moderate relative glycemic response in thebloodstream, which can be beneficial for diabetes patients. “Control” inthis context should be understood as a relative term; i.e., the glycemicresponse can be improved relative to that occurring when the same mammalconsumes a similar food product that does not contain suchdigestion-resistant and/or slowly digestible components, although theglycemic response may not necessarily be equivalent to what would beobserved in a mammal that does not suffer from diabetes.

Certain embodiments of the invention can be further understood from thefollowing examples.

Example 1

Raffinate syrup was obtained from a plant in which corn starch was beingprocessed into high fructose corn syrup. The raffinate was produced by achromatographic separation, and comprised primarily fructose anddextrose. The raffinate was subjected to nanofiltration using a DesalDK1812C-31D nanofiltration cartridge at about 500 psi of pressure and ata temperature of 40-60° C. The retentate from the nanofiltration wasdecolorized with activated charcoal, and then evaporated toapproximately 80% dry solids. A saccharide analysis of the dry productwas performed by HPAE-PAD chromatography, and the results are shown inTable 1.

TABLE 1 Component Wt % d.s.b. dextrose 38.9% fructose 6.1% isomaltose14.3% maltose 10.5% maltotriose 0.3% panose 9.5% linear highersaccharides 0.0% nonlinear higher 20.4% saccharides

This material, termed Light Raffinate, was tested for digestibilityusing an Englyst assay. About 600 mg of carbohydrate d.s.b. was added to20 mL of 0.1 M sodium acetate buffer in a test tube. The contents weremixed and then heated to about 92° C. for 30 minutes, then cooled to 37°C. Then 5 mL of enzyme solution was added to the test tube and it wasagitated by shaking in a water bath at 37° C. Small samples were removedat both 20 min and 120 min. The enzyme was inactivated, the samples werefiltered and measured for digestibility using a glucose test from YSIInc. A Heavy Raffinate, processed in a separate but similarnanofiltration operation, was also tested using the same assay. TheHeavy Raffinate contained 25-35% dry solids, as opposed to 15-25% drysolids for the Light Raffinate, but both had approximately the samepercentage of low molecular weight saccharides. A cooked potato starch,which had not been nanofiltered, was also tested as a comparison. Theresults of the digestibility assay and a saccharide analysis are shownin Table 2. Cooked potato starch is included in Table 2 for comparison.All percentages in Table 2 are on a d.s.b.

TABLE 2 % mono- % oligo- % rapidly % slowly saccharides saccharidesmaterial digestible digestible % resistant (by HPAE) (by HPAE) Lightraffinate 45 3 52 45 55 Heavy raffinate 41 3 56 44 56 Potato starch 7811 11 44 56 (cooked)

There was an excellent correlation between the percentage ofoligosaccharides in the material and the percentage of the material thatwas resistant to digestion.

Example 2

About 1,025 L of raffinate syrup at 21.4% dry solids was obtained from aplant in which corn starch was being processed into high fructose cornsyrup. The raffinate was produced by a chromatographic separation, andcomprised primarily fructose and dextrose. The raffinate was subjectedto nanofiltration using two Desal NF3840C-50D nanofiltration cartridgesat about 500 psi of pressure and at a temperature of 40-60° C. After thestarting volume was reduced by about a factor of 20, the retentate wassubjected to about 2 volumes of constant volume diafiltration using DIwater. After diafiltration, 27.6 kg of retentate product (at 33.8% ds)was collected. This material was decolorized with activated carbon (0.5%by weight of syrup solids) by stirring in a refrigerator overnight. Thisslurry was sterilized by filtration through a 0.45 micron hollow fiberfiltration cartridge, and evaporated in parts to an averageconcentration of about 73% ds.

A saccharide analysis of the dry product was performed by HPAE-PADchromatography, and the results are shown in Table 3.

TABLE 3 Component Wt % d.s.b. dextrose 4.5% fructose 0.9% isomaltose20.6% maltose 23.5% maltotriose 0.4% panose 20.9% linear highersaccharides 0.0% nonlinear higher 29.1% saccharides

Example 3—Preparation of Non-Linear Oligomers from Dextrose by Enzyme

Concentrated dextrose syrups having solids concentrations of 74%, 79.5%,and 80% were prepared by (1) evaporating diluted syrup or (2) addingwater to dextrose powder. Each dextrose/water mixture was placed in asuitable container and heated to 60° C. in a water bath.

Glucoamylase enzyme (Dextrozyme or Spirizyme, from Novozymes A/S) wasadded to the syrup—approximately 400 μl enzyme to 30 ml syrup. The syrupcontainer was capped, and then shaken vigorously to distribute theenzyme. The syrup was returned to the 60° C. water bath.

The change in sugar distribution was monitored over time by transferring2-4 ml syrup to a small glass vial, and heating it in a heated block toapproximately 85-90° C. to deactivate the enzyme.

The concentration of various sugar species was determined by HighPerformance Anion Exchange with Pulsed Amperometric Detection,(HPAE-PAD). A Dionex ion chromatograph, DX500, equipped withelectrochemical detector and gradient pump, was used for the analyses.The sugars were separated on Dionex Carbopac PA1 analytical and guardcolumns with gradient delivery of a sodium hydroxide and sodium acetateeluent. The sugars were detected using a gold electrode with afour-potential waveform. Samples were diluted with water and passedthrough Amicon Ultra-4 centrifugal filter devices before analysis.

FIG. 2 illustrates the relative amounts of dextrose, isomaltose and“non-linear highers” (which in this figure refers to nonlinear oligomershaving a degree of polymerization of four or more) in syrups of threedifferent initial dextrose compositions treated with 1.3% vol/volDextrazyme, a commercial glucoamylase enzyme from Novozymes, for 48 hrsat 60° C. As syrup concentration increased, the amount of monomericdextrose, relative to other sugars, decreased, and the amount ofnon-linear higher oligomers increases.

Example 4—Preparation of Oligomer Syrup from Corn Syrups

Starting substrates were obtained having a range of extents ofconversion, from dextrose greens (95% dextrose) to lightly convertedStaley 200 syrup (26 DE, 5% dextrose) and including high (34%) maltosesyrup, Neto 7300. The specific products used as starting materials inthis example were Staley® 200, Staley® 300, Staley® 1300, Neto® 7300,and Sweetose® 4300 corn syrups, and Staleydex® 3370 dextrose. Some ofthe characteristics of these materials are given in Table 4.

TABLE 4 Characteristics of starting syrups Staley Staley Staley NetoSweetose Staleydex 200 300 1300 7300 4300 3370 Degree of conversion verylow low regular regular high high Type of conversion acid- acid acidacid- acid- acid- enzyme enzyme enzyme enzyme Dextrose equivalent 26 3543 42 63 95 (D.E.) % % dextrose 5 13 19 9 37 90 % maltose 8 10 14 34 294 % maltotriose 11 11 13 24 9 2 % higher saccharides 76 66 54 33 25 —

While many of the less-converted syrups have substantial quantities ofnonlinear higher oligomers having a degree of polymerization of four ormore (NL DP 4+), they also have substantial quantities of linearoligomers. Several of these syrups contain measurable linear oligomersup through DP 17. FIG. 3 shows the initial saccharide distributions.

The enzymes used were Spirizyme Plus FG and Dextrozyme DX 1.5×glucoamylases and Promozyme D2 pullulanase (supplied by Novozymes), CG220 Cellulase and Transglucosidase L-500 (supplied by Genencor),Glucoamylase GA150 (supplied by Sunson Industry Group), andTransglucosidase L (supplied by Bio-Cat Inc.).

The various corn syrups were adjusted to approximately 70% ds.Approximately 3.3% (v/v) Spirizyme Plus FG Enzyme was added to each in50 ml tubes. The syrups were heated in 60° C. water baths forapproximately 4 days. The enzyme was deactivated by heating the syrupsto approximately 85° C. for 10 min. FIG. 4 shows the final saccharidedistributions. All the syrups reached a comparable sugar distribution bythe end of the four day treatment. After reversion, very little linearoligomers remained, and non-linear oligomer content had increased.

Several points should be noted. First, the reverted Staleydex 3370 syruphas a somewhat higher dextrose content and lower content of non-linearoligomers than the other syrups. While all syrups were adjusted toapproximately 70% ds before reversion, the less converted syrups, withlow initial dextrose content, consumed water as the new distribution wasestablished, and final concentrations were 4-9 percentage points higherthan the reverted 3370 syrup. (The hydrolysis of a single DP6 oligomerof dextrose to six dextrose molecules, for example, consumes five watermolecules.) As Table 5 shows, the water contents of the reverted syrupstrend with the dextrose content, and trend inversely with the higheroligomer content.

TABLE 5 Concentrations After Reversion, % Starting Syrup Water DextroseNL DP4+ Staydex 3370 28 54 23 Sweetose 4300 25 49 27 Neto 7300 21 48 27Staley 1300 24 48 27 Staley 300 19 47 27 Staley 200 20 46 28

Lower water content drives the equilibrium toward a higher concentrationof reversion products. If the water content had been adjusted so thatfinal water contents had been identical, we believe the sugardistributions would also have been identical.

Second, all syrups after reversion had much higher percentages ofbranched oligomers at each degree of polymerization (DP) than linearoligomers. Compare the relative amount of maltose vs. isomaltose, panosevs. maltotriose, and NL DP4+vs. linear oligomers of DP4 and greater (ofwhich there is virtually none remaining after reversion).

FIG. 5 shows the change in maltose and isomaltose concentrations overtime when a concentrated dextrose syrup was treated with Spirizyme. Itwould appear that linear oligomers arc the kinetic products whilenon-linear oligomers arc the thermodynamic products. That is, formingthe linear dimer, maltose, from dextrose is a rapid and reversiblereaction with low activation energy. Forming the non-linear dimer,isomaltose, is a slower reaction, and its reverse reaction has a highactivation energy.

FIGS. 6 and 7 show the change in maltose and isomaltose concentrationsover time when 70% dextrose syrup is treated with differentconcentrations of Spirizyme enzyme at 60° C.

In the treatment of Staley 1300 syrup with glucoamylase, the linearoligomers of DP 3 and greater were rapidly consumed and converted todextrose. The concentration of these linear oligomers reached itsequilibrium of about 1% of total sugars (at 70% syrup concentration,0.13% Spirizyme and 60° C.) within the first few hours of treatment.(See FIG. 8.) Over a longer period, dextrose concentration slowlydecreased, and the concentration of non-linear oligomers slowlyincreased. The change in concentration of maltose and isomaltose overtime mirrors that seen for dextrose reversion (FIG. 7).

Samples from the above experiments were heated above 85° C. for 10-20minutes to deactivate the enzymes before diluting for ion chromatographyanalysis. Had the samples been diluted in the presence of active enzyme,they might have been hydrolyzed back to dextrose.

Samples of the reverted syrups were diluted to 20% solids. A portion ofeach was held in the presence of Spirizyme enzyme at 60° C. and anotherportion of each was held in the presence of Spirizyme at 40° C. Thesyrups were sampled over time, and the enzymes in each sample weredeactivated as described above.

FIG. 9 shows the results. At 60° C., the concentration of nonlinearhigher oligomers (DP3 and greater) dropped to half within 3 hours andappeared to plateau at about 11.6% of total sugars by 7 hours. Lowertemperature slowed hydrolysis. As FIG. 9 shows, dextrose contentincreased as a result of hydrolysis. The rate of hydrolysis when twodifferent glucoamylases (Spirizyme and Dextrozyme) were used wasidentical.

It appears from these experiments that the non-linear oligomers formedthrough reversion are not immune to hydrolysis by glucoamylase enzymes(or impurities therein). However, it appears that a portion of them isresistant to hydrolysis. At 20% ds the equilibrium between monomer andoligomer is well on the side of monomer. Yet 11.3% DP4+ and 11.6% DP3+remain after 7 hours at optimum temperature for glucoamylase activity.Compare this with the virtually complete conversion of linear oligomersto dextrose in the same time frame while at much higher solids (70% ds)and half the glucoamylase content, illustrated in FIG. 8. It wouldappear that, while glucoamylase enzymes can hydrolyze non-linearoligomers, the hydrolysis is not rapid, and may not go to completeconversion. We propose that the digestive enzymes in the human gut willhave similarly reduced activity towards these compounds.

Table 6 shows the change in concentration of all sugar species whenreverted syrup was diluted to 20% ds at 60° C. in the presence of activeSpirizyme enzyme

TABLE 6 hr % of total sugars time Glucose Isomaltose Maltose PanoseMaltoriose L DP3+ NL DP3+ NL DP4+ 0 46.7 16.8 4.5 2.4 0.3 1.0 30.5 28.11 58.6 18.1 2.0 0.6 0.1 0.6 20.1 19.5 2 64.0 17.0 2.3 0.5 0.1 0.5 15.314.9 3 68.6 15.3 2.1 0.4 0.1 0.4 12.8 12.4 4.75 69.6 14.7 2.1 0.3 0.10.5 12.2 11.9 7 72.3 13.0 1.9 0.3 0.1 0.5 11.6 11.3 (“L DP3+” refers tolinear oligomers having a degree of polymerization of three or more. “NLDP3” refers to nonlinear oligomers having a degree of polymerization ofthree or more. “NL DP4+” refers to nonlinear oligomers having a degreeof polymerization of four or more.)

Regardless of starting sugar distribution or degree of conversion, allcorn syrups tested were converted to a comparable sugar distribution byglucoamylase if treated at comparable syrup concentrations.

From these experiments, it appears that during the enzymatic reversionof corn syrup, linear oligomers are rapidly hydrolyzed to dextrose. Overlonger times and at high syrup concentrations the dextrose is consumedas non-linear oligomers are formed. The production of non-linearoligomers is at least partially reversible, as evidenced by theirhydrolysis by glucoamylase at lower syrup solids. Thus, when thereverted syrups are diluted before deactivating the glucoamylase, aportion of, but apparently not all of the oligomers are hydrolyzed backto dextrose monomer. This demonstrates that the formation of non-linearlinkages by glucoamylase (or perhaps impurities it contains) is notentirely irreversible “mistakes” by the enzyme.

Example 5—Quality of Glucoamylases Impacts Reversion

The amount of enzyme needed to effect the reversion is high relative totypical enzymatic processes. Approximately 1.5% v/v of commonly usedglucoamylases (for example, Spirizyme Plus FG and Dextrozyme DX 1.5×,supplied by Novozymes) are needed to reach 80% of equilibrium reversionin 24 hrs at 60-75° C. It should be noted that enzyme manufacturers havemade great strides in reducing the tendency of the glucoamylase to formreversion products—improvements driven by the consumers of theseenzymes—the manufacturers of corn syrup—for which reversion products area bane. It is our belief that the enzymes from the 1950s would be muchmore efficient for forming these non-linear oligomer syrups than currentglucoamylases.

Lending support to the concept that “impurities” still in thesecommercial glucoamylases may be responsible for the reversion productsin the experiments reported here is the fact that, while Novozymesreports the optimum temperature for activity for both Spirizyme andDextrozyme to be 59-61° C., the rate of generation of reversion productsincreases when temperature is increased from 60 to 65° C. FIGS. 10 and11 show the rate of formation of isomaltose and non-linear oligomers ofDP 3 and greater (NL DP3+), as a function of temperature, for Spirizymeand Dextrozyme. The substrate syrup was Staley 1300, and the amount ofenzyme used was 2.7% v/v.

Example 6—Acid-Catalyzed Restructuring of Corn Syrup to Form Non-LinearOligomers

Staley 1300 syrup was diluted 1:4 with deionized water to facilitate pHdeterminations. The amount of acid (HCl or H₂SO₄) to drop syrup pH tothe pH target was determined. In one experiment, 10% Krystar crystallinefructose was added to the syrup prior to acid treatment.

Staley 1300 syrup was heated to approximately 60° C. in 50 ml screw-capcentrifuge tubes in a shaking water bath. The pre-determined amount ofacid needed to reach target pH was added to the syrup. The syrup tubeswere shaken vigorously to uniformly distribute the acid. The tubes werereturned to the water bath, and bath temperature adjusted as needed.Treatments were performed at 60, 70, and 80° C., and at pHs of 1.2, 1.8and 2.3. To monitor the progress of the reactions, portions of the syrupwere removed from tubes and neutralized by adding a caustic solution.

The caustic solutions were prepared such that a volume of causticsolution was sufficient to neutralize an equal volume of acidifiedsyrup. Approximately 80% of this volume was added all at once, whichdiluted the syrup sufficiently for pH measurement. Additional causticsolution was added dropwise until pH reached >5.0 (and preferably nogreater than 6.5).

The syrup solutions were analyzed using ion chromatography. In additionto a RSO Oligosaccharide column from Phenomenex, some samples were alsoanalyzed using a Dionex CarboPac PA200 column.

The first acid condensation reaction on Staley 1300 syrup was at pH 2.3with sulfuric acid, at 60° C. The proportion of linear oligomersdecreased, and non-linear oligomers increased.

FIG. 12 compares the changes in sugar distributions in Staley 1300 syrupcaused by acid treatment and glucoamylase treatment (both at 60° C.). Itcan be seen that the processes proceed differently. Spirizymeglucoamylase consumes linear oligomers very rapidly, generatingdextrose. With Staley 1300 syrup, the concentration of linear oligomersof DP3 and greater drops from approximately 42% of total sugars to itsequilibrium value of approximately 1% within hours of contact with theenzyme. Over a longer period, a portion of the dextrose is converted tonon-linear oligomers. The concentration of non-linear DP3 and higher(DP3+) increases over about 30 hours (under the conditions of thisenzyme treatment).

In contrast, on contact with acid, linear oligomers are consumed andnon-linear oligomers formed at comparable rates. Dextrose concentrationincreases very slowly over the course of the treatment.

In a parallel experiment, 10% dry fructose was added to Staley 1300syrup, so that the final syrup solids concentration was approximately90%. It was treated to the same pH, temperature and time as the Staley1300 syrup by itself. While the Staley 1300 syrup developed color overthe course of the treatment, the fructose-containing syrup turnedcoffee-colored almost immediately. IC analysis of samples pulled from itshowed the rate of linear oligomers reduction, and non-linear oligomersgeneration, comparable to the acid-treated syrup by itself. Fructosecontent was not significantly altered.

A second round of acid treatments was conducted in which Staley 1300syrup was adjusted to 1.2 and 1.8 pH with HCl. Each pH treatment was runat temperatures of 70° C. and 80° C. All syrups generated significantcolor over the course of the treatments. The extent of color increasedwith decreasing pH, increasing temperature and increasing time. At theextreme, darkly-colored insoluble components formed.

As FIG. 13 illustrates, the product of acid-treated syrup is a verybroad distribution of sugar oligomers. It also shows a much higherconcentration of oligomers of DP3 than the enzyme reverted syrup. Also,the acid-treated syrup contains sugars which do not appear in theenzyme-treated syrup. This is expected since the acid-catalyzedcondensations can occur between any two hydroxyl groups, whereasenzymatic condensations are typically very specific in how two sugarunits are joined together.

A Dioncx CarboPac PA200 column was used for ion chromatographicseparation of the sugars. FIG. 14 shows a chromatographic trace of anacid-treated syrup resolved by this column. It clearly shows fourcomponents in the DP2-3 range that elute separately from maltose,isomaltose, maltotriose and panose. (These four all elute beforemaltose.) It also shows a number of peaks for unidentified higheroligomers.

Table 7 below shows changes in sugar distribution over time for thesefour lower-pH, higher-temperature treatments, using the PA200 column.(The last column in the table shows the amount of the “unknown 1-4”peaks, and is not included in the NL DP3+).

TABLE 7 % of total sugars C. hr NL L NL pH temp time color Glucose DP3+DP3+ DP2-3? 1.8 70 0 white 22 23 42 0 1.8 70 4 white 27 27 28 1.7 1.8 708 white 28 29 25 2.8 1.8 70 24 white 34 30 13 7.3 1.8 70 48 tan 37 304.7 14 1.2 70 0 white 22 23 42 0 1.2 70 4 white 33 30 15 5.9 1.2 70 8tan 36 30 6.6 12 1.2 70 24 tea 36 30 0.5 20 1.2 70 48 coffee 35 29 0.321 1.8 80 0 white 22 23 42 0 1.8 80 4 white 39 28 1.6 18 1.8 80 8 tan 3629 0.7 21 1.8 80 24 tea 35 30 0.5 20 1.8 80 48 coffee 35 29 0.4 20 1.280 0 white 22 23 42 0 1.2 80 4 tan 29 33 18 4.5 1.2 80 8 tea 32 32 118.6 1.2 80 24 coffee + 37 31 0.5 18 insol 1.2 80 48 coffee + 33 32 0.221 insol

Example 7—Enzyme Reversion—High Sugar

Approximately 35 gal of 43 DE corn syrup at 80% dry solids (Staley 1300)with an additional 5 gal of deionized water was slowly agitated in atank and heated to a temperature of 60° C. About 1.6 gal of SpirizymePlus FG enzyme was added to the syrup slowly and with good agitation.After 24 hours at 60° C., the syrup was heated to 85° C. and held for 20minutes. The syrup was then diluted from 70% to 20% dry solidsconcentration by adding 100 gal water. The sugar solution was subjectedto nanofiltration using a Desal NF3840C 30D nanofiltration cartridge atabout 500 psi of pressure and at a temperature of 55-60° C. Freshdiafiltration water was added to maintain permeate flux in the range of2 to 10 LMH. Filtration continued until the retentate contained lessthan 5% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis. The nanofiltration retentate was treated with 1% activatedcarbon on a dry solids basis. Next, the carbon was removed by filtrationand the filtrate evaporated to 80.2% ds.

A saccharide analysis of the final product was performed by HPAE-PADchromatography, and the results are shown in Table 8.

TABLE 8 Component Wt % d.s.b. dextrose 1.1% fructose 0.1% isomaltose27.7% maltose 5.2% maltotriose 0.3% panose 3.2% linear highersaccharides 3.3% nonlinear higher 59.1% saccharides(“Higher saccharides” in the above table means oligomers having a DP ofthree or more.)

Example 8—Enzyme Reversion—Low Sugar

Approximately 35 gal of 43 DE corn syrup at 80% dry solids (Staley 1300)with an additional 5 gal of deionized water was slowly agitated in atank and heated to a temperature of 60° C. About 1.6 gal of SpirizymePlus FG enzyme was added to the syrup slowly and with good agitation.After 24 hours at 60° C., the syrup was heated to 85° C. and held for 20minutes. The syrup was then diluted from 70% to 20% dry solidsconcentration by adding 100 gal water. The sugar solution was subjectedto ultrafiltration using a Desal UF-1 3840C 50D ultrafiltrationcartridge at about 400 psi of pressure and at a temperature of 55-60° C.Fresh diafiltration water was added to maintain permeate flux in therange of 10 to 20 LMH. Filtration continued until the retentatecontained less than 1% dextrose (d.s.b.) by combination of Karl Fisherand YSI dextrose analysis. The ultrafiltration retentate was treatedwith 1% activated carbon on a dry solids basis. Next, the carbon wasremoved by filtration and the filtrate evaporated to 73.4% ds.

A saccharide analysis of the final product was performed by HPAE-PADchromatography, and the results are shown in Table 9.

TABLE 9 Component Wt % d.s.b. dextrose 1.0% fructose 0.1% isomaltose6.0% maltose 7.5% maltotriose 0.4% panose 4.4% linear higher saccharides7.2% nonlinear higher 73.3% saccharides

Example 9—Enzyme Reversion—High Isomaltose

The syrup from Example 7 was subjected to ultrafiltration using a DesalUF-1 3840C 50D ultrafiltration cartridge at about 400 psi of pressureand at a temperature of 55-60° C. The permeate from this operation wasthen subjected to nanofiltration using a Desal NF3840C 30Dnanofiltration cartridge at about 500 psi of pressure and at atemperature of 55-60° C. Fresh diafiltration water was added to maintainpermeate flux in the range of 2 to 10 LMH. Filtration continued untilthe retentate contained less than 5% dextrose (d.s.b.) by combination ofKarl Fisher and YSI dextrose analysis. The nanofiltration retentate wastreated with 1% activated carbon on a dry solids basis. Next, the carbonwas removed by filtration and the filtrate evaporated to 90.2% ds.

A saccharide analysis of the final product was performed by HPAE-PADchromatography, and the results are shown in Table 10.

TABLE 10 Component Wt % d.s.b. dextrose 2.8% fructose 0.0% isomaltose70.8% maltose 6.5% maltotriose 0.1% panose 0.6% linear highersaccharides 0.0% nonlinear higher 19.2% saccharides

Example 10—Acid Reversion—Moderately Resistant

Approximately 35 gal of 43 DE corn syrup at 80% dry solids (Staley 1300)was slowly agitated in a tank and heated to a temperature of 80° C.About 4.1 lb 37% hydrochloric acid was added to the syrup slowly andwith good agitation. The reaction was maintained at approximately 80%dry solids concentration, as measured by Karl Fischer analysis throughperiodic additions of water. After 24 hours, heating was discontinuedand approximately 35 gal of 0.35% sodium hydroxide solution was addedslowly and with good agitation. Next, pH was adjusted to 5.0 and waterwas added to reach a final sugar concentration of 30% d.s. The sugarsolution was subjected to ultrafiltration using a Desal UF-1ultrafiltration cartridge at about 400 psi of pressure and at atemperature of 55-60 C. Fresh diafiltration water was added to maintainpermeate flux in the range of 10 to 20 LMH. Filtration continued untilthe retentate contained less than 5% dextrose (d.s.b.) by combination ofKarl Fisher and YSI dextrose analysis. The ultrafiltration retentate wastreated with 2% activated carbon on a dry solids basis. Next, the carbonwas removed by filtration and the filtrate evaporated to 71.5% ds.

A saccharide analysis of the final product was performed by HPAE-PADchromatography, and the results arc shown in Table 11.

TABLE 11 Component Wt % d.s.b. dextrose 6.4% fructose 0.1% isomaltose1.6% maltose 3.8% maltotriose 4.3% panose 3.8% linear higher saccharides25.6% nonlinear higher 54.9% saccharides

Example 11—Acid Reversion Followed by Hydrogenation

Approximately 35 gal of 63 DE corn syrup at 80% dry solids (SWEETOSE®4300) was slowly agitated in a tank. Then 37% hydrochloric acid wasadded slowly with good agitation to give 0.25% (w/w) HCl with respect tosyrup dry solids. The mixture was then heated to a temperature of 80° C.The reaction was maintained at approximately 80% dry solidsconcentration, as measured by Karl Fischer analysis through periodicadditions of water. After 16 hours, heating was discontinued and pH wasadjusted to 4.5 using 0.35% sodium hydroxide solution. Additional waterwas added to reach a final sugar concentration of 30% d.s. The sugarsolution was subjected to ultrafiltration using a Desal UF-1ultrafiltration cartridge at about 400 psi of pressure and at atemperature of 55-60° C. Fresh diafiltration water was added to maintainpermeate flux in the range of 10 to 20 LMH. Ultrafiltration continueduntil the retentate contained less than 10% dextrose (d.s.b.) bycombination of Karl Fisher and YSI dextrose analysis. Theultrafiltration retentate was subjected to nanofiltration using a DesalNF3840C 30D nanofiltration cartridge at about 500 psi of pressure and ata temperature of 55-60° C. Fresh diafiltration water was added tomaintain permeate flux in the range of 2 to 10 LMH. Filtration continueduntil the retentate contained less than 1% dextrose (d.s.b.) bycombination of Karl Fisher and YSI dextrose analysis. The nanofiltrationretentate was treated with 1% activated carbon on a dry solids basis.Next, the carbon was removed by filtration and the filtrate evaporatedto 73.5% ds.

Dextrose Equivalence (DE) for this product was measured by AOAC method920.51 (Lane Eynon) and was found to be 21 DE. A saccharide analysis ofthis product was performed by HPAE-PAD chromatography, and the resultsare shown in Table 12.

TABLE 12 Component Wt % d.s.b. dextrose 1.4% fructose 0.1% isomaltose0.0% maltose 4.3% sorbitol 0.0% panose 6.3% linear higher saccharides12.6% nonlinear higher 75.2% saccharides

This product was further subjected to hydrogenation reaction conditions.About 1.5 kg of a 43% d.s. solution of the material described in table 9was introduced into a pressure reactor and 6.45 grams of 5% ruthenium oncarbon catalyst was added with stirring to give 0.05% ruthenium (w/w) onsyrup dry solids. The reactor was closed, purged with nitrogen gas, andthen pressurized with hydrogen gas to a pressure of 600 psi. The reactorwas then heated to 120° C. This temperature and a hydrogen pressure of600-650 psi was maintained for four hours. The reaction vessel wascooled, carefully vented and purged with nitrogen. The reaction productwas then filtered through diatomaceous earth to give a clear colorlesssolution.

Dextrose Equivalence (DE) for this product was measured by AOAC method920.51 (Lane Eynon) and was found to be 5 DE. A saccharide analysis ofthis product was performed by HPAE-PAD chromatography, and the resultsare shown in Table 13.

TABLE 13 Component Wt % d.s.b. dextrose 3.1% fructose 0.2% isomaltose0.0% maltose 5.9% sorbitol 3.0% panose 5.6% linear higher saccharides9.5% nonlinear higher 72.7% saccharides

Example 12—Englyst Digestion Assay

The product materials from Examples 7, 8 and 10, were tested fordigestibility using an Englyst assay. About 600 mg of carbohydrated.s.b. was added to 20 mL of 0.1 M sodium acetate buffer in a test tube.The contents were mixed and then heated to about 92° C. for 30 minutes,then cooled to 37° C. Then 5 mL of enzyme solution was added to the testtube and it was agitated by shaking in a water bath at 37° C. Smallsamples were removed at both 20 min and 120 min. The enzyme wasinactivated; the samples were filtered and measured for digestibilityusing a dextrose test from YSI Inc. A 10 DE maltodextrin (STAR-DRI 10),known to be very digestible, was also tested as a comparison. Theresults of the digestibility assay and a saccharide analysis are shownin Table 14. A 10 DE maltodextrin is included in Table 5 for comparison.All percentages in Table 14 are on a d.s.b.

TABLE 14 % non-linear % rapidly % slowly highers material digestibledigestible % resistant (by HPAE) Example 7 4.2 10.2 85.6 59.1 Example 85.2 10.0 84.8 73.3 Example 10 24.8 5.5 69.8 54.9 10 DE maltodextrin 89.73.4 7.0 13.7(“Highers” in Table 14 refers to oligomers having a degree ofpolymerization of three or more.)

There was an excellent correlation (R²=0.95) between the percentage ofnon-linear highers in the material and the percentage of the materialthat was resistant to digestion.

Example 13—Hard Candy, Lemon Flavored

980 grams (d.s.b.) of Example 7 (Enzyme Reversion—High Sugar) was addedto a pot and cooked on a stove to an internal temperature of 300° F.Next, 15 grams of citric acid and 1.2 grams of sucralose were added withstirring. Then, yellow color and lemon flavor were added and the mixturewas poured into candy moulds. The hard candy was formed upon cooling toroom temperature.

Example 14—Jelly Candy, Grape Flavored

840 grams of Example 8 (Enzyme Reversion—Low Sugar) was added to amixing bowl. Purple color and grape flavor was added to taste. Next, 160grams of MiraThik 468 instant starch was added in portions withmoderately vigorous mixing. The jelly candy was formed after cooling toroom temperature over 20 minutes.

Example 15—Yogurt

900 grams of milk (2% fat) was added to a pot on a stove. Next 80 grams(d.s.b.) of Example 10 (Acid Reversion—Moderately Resistant) was addedwith stirring. Then the mixture was heated to a target temperature of150° F. As the mixture was heating, 20 grams of Rezista 682 starch wasadded in portions with mixing. After the mixture reached an internaltemperature of 150° F., it was held for five minutes, then passedthrough a two stage homogenizer (1500/500 psi). The product was nextpasteurized at 190° F. for 5 minutes. Then the mixture was cooled to 90°F. and inoculated with active yogurt cultures. The incubation wasallowed to continue until the yogurt reached a pH of 4.5, then it wasrefrigerated prior to consumption.

Example 16

The following general procedures were used to prepare samples ofdigestion-resistant corn syrups in accordance with the presentinvention. In the preparation of some low sugar samples, nanofiltrationwas run to less than 1% dextrose, instead of 5% as described in thegeneral procedures below.

Sample 1—Oligomer Syrup from HFCS Raffinate

1. Transfer mixed raffinate from high fructose corn syrup (HFCS) processto filtration unit and concentrate volume by 10× to 30× with Desal UF-1membrane. Note: this step is optional, depending on the final DP2target.

2. Switch filtration membrane to nanofiltration (Desal NF3840C 30D“DL”). Add fresh diafiltration water at a rate to maintain permeate fluxin the range of 2 to 10 LMH. Continue until retentate contains less than5% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis.

3. Collect retentate product and add 1% activated carbon on a dry solidsbasis. Refrigerate.

4. Remove carbon by filtration and evaporate filtrate to >70% ds.

Sample 2—Oligomer Syrup from Dextrose Greens

1. Transfer diluted dextrose greens (at 20-30% ds) to filtration unitand concentrate volume by 10× to 30× with Desal UF-1 membrane. Note:this step is optional, depending on the final DP2 target.

2. Switch filtration membrane to nanofiltration (Desal NF3840C 30D“DL”). Add fresh diafiltration water at a rate to maintain permeate fluxin the range of 2 to 10 LMH. Continue until retentate contains less than5% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis.

3. Collect retentate product and add 1% activated carbon on a dry solidsbasis. Refrigerate.

4. Remove carbon by filtration and evaporate filtrate to >70% ds.

Sample 3—Enzymatic Reversion of STALEY® 1300 Corn Syrup to Form >25%Non-Linear Oligomers of Dextrose

1. Pump 35 gal Staley 1300 syrup and 5 gal water to tank. Start agitatorand begin heating.

2. Heat syrup to 60° C. and confirm that temperature has stabilized at60° C.+/−5 C.

3. Add 1.6 gal (6.1 liter) Spirizyme Plus FG enzyme to the syrup.

4. Hold at 60° C.+/−5 C for 24 hr.

5. At the end of the 60° C./24 hr hold, heat syrup to 85-90° C. Oncesyrup temperature has stabilized above 85° C., hold for 20 min.

6. Turn off heat to tank.

7. Dilute syrup from 70% to 20% solids by adding 100 gal water (140 galtotal).

8. Transfer to filtration unit and concentrate volume by 10× to 30× withDesal UF-1 membrane.

9. Switch filtration membrane to nanofiltration (Desal NF3840C 30D“DL”). Add fresh diafiltration water at a rate to maintain permeate fluxin the range of 2 to 10 LMH. Continue until retentate contains less than1% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis.

10. Collect retentate product and add 1% activated carbon on a drysolids basis. Refrigerate.

11. Remove carbon by filtration and evaporate filtrate to >70% ds.

Sample 4—Acid-Catalyzed Restructuring of Tate & Lyle SWEETOSE® 4300 CornSyrup

1. Pump 35 gal SWEETOSE® 4300 syrup to tank. Start agitator and beginheating to 80° C.

2. Add ˜2.8 lb 37% hydrochloric acid to the syrup slowly and with goodagitation (calculated to give 0.25% HCl dry solids on syrup dry solidsin the reaction, based on assumption that 4300 syrup density is 11.9lb/gal).

3. Hold at 80% ds+/−5%. Remove a reaction sample every two hours anddilute with an equal weight of DI water. Run Karl Fischer on dilutedsample. If less than 40% ds do nothing. If greater than 40% ds, add 4 lbDI water for every 100 lb of initial reaction contents for every 1% dsover 40% ds.

4. In addition to the above samples for Karl Fischer, collect samples tobe used for monitoring the progress of the reaction. Remove these at thefollowing intervals following acid addition: 2 hr, 4 hr, 8 hr, and 16hr. After each sampling, move quickly to adjust the pH of the sample byadding an equal weight of 0.35% NaOH solution, mix well, and measure pH.Adjust sample pH as needed to bring to 5.0-6.5.

5. At the end of the 80° C./16 hr hold, discontinue heating. Add 0.35%caustic solution, slowly and with good agitation until pH is stable inthe range of 4.5-5.5.

6. Add dilution water, if needed, to reach a final solids concentrationof 30% d.s.

7. Transfer to filtration unit and concentrate volume by 10× to 30× withDesal UF-1 membrane. Note: this step is optional, depending on the finalDP2 target.

8. Switch filtration membrane to nanofiltration (Desal NF3840C 30D“DL”). Add fresh diafiltration water at a rate to maintain permeate fluxin the range of 2 to 10 LMH. Continue until retentate contains less than5% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis.

9. Collect retentate product and add 1% activated carbon on a dry solidsbasis. Refrigerate.

10. Remove carbon by filtration and evaporate filtrate to >70% ds.

Sample 5—Phosphoric and Hydrochloric Acid-Catalyzed Restructuring ofSWEETOSE® 4300 Corn Syrup

1. Pump 35 gal SWEETOSE® 4300 syrup to tank. Start agitator and beginheating to 80° C.

2. Add ˜0.35 lb 75% phosphoric acid to the syrup slowly and with goodagitation. Then add 0.10 lb 37% hydrochloric acid to the syrup slowlyand with good agitation (calculated to give 0.08% H3PO4 and 100 ppm HCldry solids on syrup dry solids in the reaction, based on assumption that4300 syrup density is 11.9 lb/gal).

3. Hold at 80% ds+/−5%. Remove a reaction sample every two hours anddilute with an equal weight of DI water. Run Karl Fischer on dilutedsample. If less than 40% ds, do nothing. If greater than 40% ds, add 4lb DI water for every 100 lb of initial reaction contents for every 1%ds over 40% ds.

4. In addition to the above samples for Karl Fischer, collect samples tobe used for monitoring the progress of the reaction. Remove these at thefollowing intervals following acid addition: 2 hr, 4 hr, 8 hr, and 16hr. After each sampling, move quickly to adjust the pH of the sample byadding an equal weight of 0.35% NaOH solution, mix well, and measure pH.Adjust sample pH as needed to bring to 5.0-6.5.

5. At the end of the 80° C./16 hr hold, discontinue heating. Add 0.35%caustic solution, slowly and with good agitation until pH is stable inthe range of 4.5-5.5.

6. Add dilution water, if needed, to reach a final sugar concentrationof 30% d.s.

7. Transfer to filtration unit and concentrate volume by 10× to 30× withDesal UF-1 membrane. Note: this step is optional, depending on the finalDP2 target.

8. Switch filtration membrane to nanofiltration (Desal NF3840C 30D“DL”). Add fresh diafiltration water at a rate to maintain permeate fluxin the range of 2 to 10 LMH. Continue until retentate contains less than5% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis.

9. Collect retentate product and add 1% activated carbon on a dry solidsbasis. Refrigerate.

10. Remove carbon by filtration and evaporate filtrate to >70% ds.

Sample 6—Acid-catalyzed restructuring of Tate and Lyle STALEY® 1300 CornSyrup

1. Pump 35 gal SWEETOSE® 1300 syrup to tank. Start agitator and beginheating to 80° C.

2. Add ˜2.8 lb 37% hydrochloric acid to the syrup slowly and with goodagitation (calculated to give 0.25% HCl dry solids on syrup dry solidsin the reaction, based on assumption that 4300 syrup density is 11.9lb/gal).

3. Hold at 80% ds+/−5%. Remove a reaction sample every 2 hours anddilute with an equal weight of DI water. Run Karl Fischer on dilutedsample. If less than 40% ds do nothing. If greater than 40% ds add 4 lbDI water for every 100 lb of initial reaction contents for every 1% dsover 40% ds.

4. In addition to the above samples for Karl Fischer, collect samples tobe used for monitoring the progress of the reaction. Remove these at thefollowing intervals following acid addition: 2 hr, 4 hr, 8 hr, and 16hr. After each sampling, move quickly to adjust the pH of the sample byadding an equal weight of 0.35% NaOH solution, mix well, and measure pH.Adjust sample pH as needed to bring to 5.0-6.5.

5. At the end of the 80° C./16 hr hold, discontinue heating. Add 0.35%caustic solution, slowly and with good agitation until pH is stable inthe range of 4.5-5.5.

6. Add dilution water, if needed, to reach a final solids concentrationof 30% d.s.

7. Transfer to filtration skid and concentrate volume by 10× to 30× withDesal UF-1 membrane. Note: this step is optional, depending on the finalDP2 target.

8. Switch filtration membrane to nanofiltration (Desal NF3840C 30D“DL”). Add fresh diafiltration water at a rate to maintain permeate fluxin the range of 2 to 10 LMH. Continue until retentate contains less than5% dextrose (d.s.b.) by combination of Karl Fisher and YSI dextroseanalysis.

9. Collect retentate product and add 1% activated carbon on a dry solidsbasis. Refrigerate.

10. Remove carbon by filtration and evaporate filtrate to >70% ds.

Some of the syrups prepared by these methods were used in the subsequentexamples, where they are referenced by sample number.

Example 17

A breakfast cereal comprising an oligosaccharide composition accordingto the present invention can be prepared as described below. The cerealcomprises an extruded portion and a coating placed on the extrudedportion. The composition of the extruded portion can be as follows (byweight percent):

Corn Meal 54.80 Whole Wheat Flour 25.19 Resistant Corn Syrup Solids(Sample 5) 13.51 Whole Oat Flour 5.00 Vitamin blend 0.50 Salt 1.00 Total100.0

The extruded portion is prepared using the following steps: Uniformlymix ingredients together in a mixer/blender. Feed the dry blend andwater to achieve target extrusion moisture. Use typical extrusion anddrying conditions. Cool and package.

The coating composition is a 75% solids solution of 50% sugar, 50%resistant corn syrup. It is prepared using the following steps: Placespray gun in convection oven at 250° F. to preheat. Weigh outapproximately 100 g of cereal and place into tumbler that has been firstcoated with oil based release agent. Blend the dry ingredients (75%total dry solids) in kettle. Add water and mix. Heat the syrup toapproximately 230° F. (rapid boil). Weight out the desired amount ofsyrup needed to give the correct ratio of cereal:coating to achieve theappropriate ratio (approximately 45-50% coating by final weight of thecereal). Pour the syrup into the pre-heated spray gun and attach the airline hose to the spray gun. As the cereal is tumbling, spray the syruponto the cereal until all of the syrup has been applied. After desiredamount of coating is applied, allow coated cereal to tumble in enrobingdrum for three minutes to insure an even coating. Pour the coated cerealout onto a baking sheet that has been sprayed with release agent. Drythe cereal in convection oven at 250° F. for six minutes or until cerealappears dry. Stir halfway through drying to prevent cereal from stickingto the pan and clumping of the cereal. After drying, allow cereal tocool for five minutes. After cooling, weigh the cereal to determine thepercent coating. Package cereal in plastic storage bag.

Example 18

Yogurt comprising an oligosaccharide composition according to thepresent invention was prepared.

The ingredients were:

2% milk 3614 Non fat dry milk (NFDM) 133 Resistant corn syrup (Sample 5)200 Rezista 682 starch 53 Total weight: 4000 g

The yogurt was prepared using the following steps: Disperse dryingredients into liquid ingredients using a pump and funnel orliquefier. Preheat to 150° F. Homogenize at 1500/500 psi using a twostage homogenizer. Pasteurize at 190° F. for 5 minutes. Cool to 90° F.and add culture. Culture to finished pH 4.4. Stir the product and beginto cool to stop active culture growth. Package and cool.

Example 19

A yogurt drink comprising an oligosaccharide composition according tothe present invention was prepared.

The ingredients were:

Skim Milk 94.21 Whey protein concentrate 1.2 Resistant corn syrup(Sample 5) 4.25 Stabilizer blend 0.442 Sucralose solution 0.008 Total100.0

The yogurt drink was prepared using the following steps: Add dryingredients to liquid using a pump and funnel or liquefier. Preheat to150° F. Homogenize at 1500/500 psi using a two stage homogenizer.Pasteurize at 190° F. for 5 minutes. Cool to 90° F. and add culture.Culture to finished pH 4.4. Break, package and cool.

Example 20

A frozen novelty comprising an oligosaccharide composition according tothe present invention can be prepared as described below.

The ingredients are:

Ingredients % Butterfat 1.20% Milk solids, nonfat 11.75% (MSNF) Sucrose10.70% Resistant corn 6.70% syrup (Sample 5) Whey Protein 34 2.00%Polydextrose 4.10% Stabilizer Blend 0.67% Total Solids 37.12% Weight perGallon 9.63 lbs

The frozen novelty can be prepared using the following steps:Standardize cream, milk and nonfat dry milk to desired butterfat andmilk-solids, nonfat (MSNF) level. Add the stabilizer to liquid sugarusing moderate agitation to ensure proper dispersion. Blend milk andliquid sugar portions thoroughly in batch tank. Incorporate milk fatsolids portion with mix and use low agitation to minimize airincorporation. Pasteurize at 185° F. for 30 seconds or the equivalenttime and temperature. Homogenize using a two stage homogenizer at 2500psi double stage (2000 and 500 psi, first and second stagerespectively). Cool mix to 34-38° F. and hold for a minimum of fourhours for aging. (Overnight aging is preferred).

Example 21

A sugarless ice cream comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Butterfat  7-12% Milk Solids Non-fat 10-12% Resistant corn syrup (Sample5) 12-15% maltodextrin 3-5% sucralose 0.0085%-0.012%   vitamin Apalmitate 0.009%, Stabilizer blend 0.40-0.50%

The sugarless ice cream was prepared using the following steps:Stabilizer blend, sucralose, vitamin A and maltodextrin are mixed inskim milk under shear. Resistant corn syrup is added to the mixtureunder shear. Cream (butterfat) is then added slowly to avoid churningand aeration. The ice cream is then pasteurized and homogenized at 175°F. for 30 seconds, 2500 psi 2 stage, respectively. The mix isrefrigerated overnight (35-40° F.) and then processed to a frozen stateusing a continuous freezing system.

Example 22

Marshmallows comprising an oligosaccharide composition according to thepresent invention were prepared.

The ingredients were prepared in three separate parts:

Part A Gelatin 250 Bloom 22.5 Cold Water 44.5 Part B Resistant cornsyrup (Sample 5, 71%) 337.5 Part C Hystar Maltitol Syrup 585.5 Total 990g

The marshmallows were prepared using the following steps: Mixingredients in Part A (gelatin into water). Preheat resistant corn syrupto 135° F. Heat maltitol syrup to 200° F. Combine Parts B and C and coolto 145° F. Melt Part A in microwave for 30 seconds to dissolve gelatin.Add Part A to other parts and whip mixture with a wire whisk in a Hobartmixer until a 0.5 density is reached. Fill marshmallow into pastry bagsand deposit into starch molds.

Example 23

A hard candy comprising an oligosaccharide composition according to thepresent invention was prepared.

The ingredients were:

Sugar 42.0 Resistant Corn Syrup (Sample 4) 43.7 Water 14.3 Total 100.0

The hard candy was prepared using the following steps: Mix sugar andresistant corn syrup with water. Heat to ca. 138° C. with Bosch cookerand vacuum for two minutes to 129° C. Add citric acid (18 g for 3 kgproduct), and flavor. Deposit or form the sweets.

Example 24

A gelatin jelly candy comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Sugar 35.2 Resistant corn syrup (Sample 5, 71%) 36.6 Water 12.3 Gelatin6.6 Water 9.3 Total 100.0

The gelatin jelly candy was prepared using the following steps: Mixgelatin and water and keep at 70° C. Mix sugar, resistant corn syrup,and water. Heat until solids reach 89% (approximately 120° C.). Cooldown to 90° C. Add gelatin solution. Add citric acid solution 50% (18g/1000 g), and flavor and color to suit. Deposit in molding starch anddry at ambient conditions to a weight percentage of dry solids (ds) of81-82%.

Example 25

A jam comprising an oligosaccharide composition according to the presentinvention was prepared.

The ingredients were:

Water 36.5 Apricots 32.8 Resistant corn syrup (Sample 5, 71%) 15.5Maltodextrin 10.2 Pectin (low methoxy) 4.58 Xanthan Gum 0.10 Citric Acid0.15 Sucralose 0.06 Potassium Sorbate 0.10 Calcium Chloride 0.01 Total100.0

The jam was prepared using the following steps: Mix dry ingredients. Adddry ingredients to liquid ingredients and fruit. Heat to 220° F. Putinto containers and cool.

Example 26

A sweetened children's beverage comprising an oligosaccharidecomposition according to the present invention was prepared.

The ingredients were:

Water 86.35 Citric Acid 0.15 Strawberry flavor 0.10 Resistant corn syrup(Sample 5, 73.4%) 13.3 Color (#40, 10%) 0.10 Sucralose 0.004

The drink was prepared using the following steps: Add ingredients slowlyinto the water using a mixer. Heat drink to 180° F. Immediately hot fillinto bottles. Place bottles in a water bath to cool.

Example 27

An orange flavored juice soda beverage comprising an oligosaccharidecomposition according to the present invention was prepared.

The ingredients were:

Ingredient % Potassium citrate 0.0200 Acid (citric, malic) 0.2000 RCS(Sample 5, 71% ds) 1.8750 High intensity sweeteners (sucralose, Ace-K)0.015 5% Clarified Val OJ Conc., 60.56 Brix 1.0177 Red #40 0.0009 Yellow#5 0.0044 Orange flavor 0.1218 Filtered water 96.7452 100

The orange juice soda was prepared using the following steps: Dry blendthe potassium citrate, acids, resistant corn syrup, and high intensitysweeteners. Blend orange juice concentrate, Red #40, Yellow #5, orangeflavor and the blend from the previous step into the water. Carbonate todesired volume of CO₂ (2-4).

Example 28

A savory high solids filling comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Ingredients Amount (g) Tate and Lyle texturizing 18.6 blend¹ Canola Oil34 Cheese Flavors 28 Resistant corn syrup solids 17 (Sample 5) Salt 1.3Jalapeno Flavors 0.75 Lactic Acid 0.2 Citric Acid 0.15 TOTAL 100 ¹Blendof food starch modified, wheat protein, and maltodextrin.

Ingredients were incorporated into the product mixture in the followingorder: (1) Canola oil, (2) Flavors, Citric Acid, Lactic Acid and Salt,(3) resistant corn syrup, and (4) Tate and Lyle Texturizing Blend.

Example 29

A high solids fruit filling comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

% Part A Isosweet 5500 H FCS 21 Mirathik 603 (food- 6 modified starch)Part B resistant corn syrup 70.88 (Sample 6) water 1.55 nat. and art.rasp. flavor 256639 0.3 (tastemaker) Part C malic acid 0.1 citric acid0.1 red color 09310 (WJ) 0.06 blue color 09918 (WJ) 0.01 100

The jam was prepared using the following steps: Place Part A ISOSWEET®5500 in a Hobart mixer. Slowly add Mirathik 603 while mixing for 1.5minutes. Add Part B resistant corn syrup, flavor, and water. Blend untiluniform (1 minute). Allow to rest for about three minutes until mixturebecomes thick. Preblend Part C ingredients and add to the mixture. Blenduntil uniform. Allow filling to set 24 hours to achieve full viscosity.

Example 30

A sheeted cracker comprising an oligosaccharide composition according tothe present invention was prepared.

The ingredients were:

Flour 70.949 Resistant corn syrup solids (Sample 5) 17.00 Shortening10.0 Sucralose 0.001 Sodium bicarbonate 0.70 Salt 0.50 Monocalciumphosphate 0.85 Total 100.00 Amount of water 30

The sheeted cracker was prepared using the following steps: Mix doughuntil all ingredients are wetted and dough is pliable. Sheet dough to1.1 mm. Cut pieces. Bake in convection oven (low fan) at 350° F. forfive minutes.

Example 31

An expanded extruded snack comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Corn flour 75.00 Resistant corn syrup solids (Sample 5) 23.50 Salt 1.50Total 100.0

The expanded extruded snack was prepared using the following steps: Mixdry ingredients. Feed dry ingredients into the extruder. Extrude intoproper shapes. Dry for 10 minutes to 1% finished moisture content.

Example 32

Tortilla chips comprising an oligosaccharide composition according tothe present invention was prepared.

The ingredients were:

Corn Chip #8 flour 23.5 Tortilla Chip #1 flour 24.0 Resistant corn syrup(Sample 5) 2.50 water 40.0 Total 100.0

The tortilla chips were prepared using the following steps: Make a 1:1mixture of Tortilla Chip #1 flour and Corn Chip #8 flour. Mix on lowspeed for one minute in Hobart mixer. Add resistant corn syrup and mixon low for one minute. With the mixer still running on low speed, slowlyadd room temperature water in a stream to the dry mixture. Once all thewater is added, increase mixer speed and mix for three minutes. Coverdough and let sit for 30 minutes in a plastic beaker. Sheet the doughusing a Rondo sheeter, and gradually roll dough to have about a 1.3 mmthickness (testing thickness by using micrometer). Use the Rondosheeter, cut the dough using the cutter by placing the doughhorizontally. Fry for approximately 1:45 to 2 minutes (until chipsappear golden brown and bubbling was almost ceased) in a fryerpre-heated to 375° F. While chips are frying use a metal spatula to stirthe chips so they are constantly being submerged on both sides (to helpeven fat absorption). Remove from fryer and let chips drain for fourminutes by hanging the basket. Pour chips onto a cloth towel and let sitfor six minutes. Bag, seal, and label the tortilla chips in a plasticbag.

Example 33

A gelatin dessert dry mix comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Resistant corn syrup solids (Sample 5) 88.66 Gelatin 250 bloom 9.00Adipic acid 0.90 Fumaric acid 0.60 Strawberry flavor 0.50 Disodiumphosphate 0.20 Color (red #40) 0.14 Sucralose 0.03

The gelatin dessert dry mix was prepared using the following steps: Mixdry ingredients. Weigh 85.1 g of dry mix and add to 226.8 g of water at212° F. Dissolve completely. Add 226.8 g of cold water and mixthoroughly. Refrigerate at least four hours.

Example 34

A snack bar comprising an oligosaccharide composition according to thepresent invention was prepared, comprising a high solids filling, abinding syrup, and an extruded piece.

The ingredients for the high solids filling were:

Part A Resistant corn syrup (Sample 6) 21.00 MiraThik 603 starch 6.00Part B Resistant corn syrup (sample 6) 80.88 Water 1.55 Raspberry flavor0.30 Part C Malic Acid 0.10 Citric Acid 0.10 Red Color 0.06 Blue color0.01 Total 100.00

The high solids filling was prepared using the following steps: Placepart A, comprising resistant corn syrup, in a mixer. Slowly add Mirathik603 while mixing on a slow speed for 1.5 minutes. Add part B (resistantcorn syrup, flavor, water) and blend until uniform (one minute on lowspeed). Allow to rest for about 3 minutes until mixture becomes thick.Preblend part C ingredients and add to mixture. Blend until uniform(allow filling to set 24 hours to achieve full viscosity.).

The ingredients for the binding syrup were:

Resistant corn syrup (Sample 2) 67.7 Glycerine 10.7 StaSlim 150 starch13.3 Shortening 7.5 Salt 0.8 Total 100.0

The binding syrup was prepared using the following steps: Combine andheat to 172° F. Add to cereal/granola pieces and combine to coat piecesevenly. Combine at a ratio of 54% syrup, 46% cereal.

The ingredients for the extruded piece were:

Corn meal 55.30 Whole wheat flour 25.19 Resistant corn syrup (Sample 2)13.51 Whole oat flour 5.00 Salt 1.00 Total 100.0

The extruded piece was prepared using the following steps: Uniformly mixingredients together in a mixer/blender. Feed the dry blend and water toachieve target extrusion moisture. Use typical extrusion and dryingconditions. Cool and package.

Binding syrup is mixed to coat extruded piece or other particulate andmixture is sheeted or formed and cut to appropriate size. High solidsfilling typically would be added between the two sheets ofbinder/particulate mixture.

Example 35

A spice cake comprising an oligosaccharide composition according to thepresent invention was prepared.

The ingredients were:

Ingredient % water 40.67 Purasnow cake flour 21.56 sorbitol 17.70 RCSsolids (Sample 5) 8.85 Mira-Thik 603 food starch modified 1.00 Core M90(maltodextrin, sucralose) 0.25 EC-25 emulsifier 2.65 Provon 190 wheyprotein isolate 1.25 HiJel S food starch - modified 0.99 dry egg whites0.99 salt 0.79 GMS 90 emulsifier 0.59 Baking soda 0.56 Pan O Lite 0.45dry vanilla 1011320 0.40 Dicalcium phosphate dihydrate 0.34 cinnamon0.29 Sodium propionate 0.21 nutmeg 0.17 xanthan gum 0.12 Durafax 60emulsifier 0.10 ground cloves 0.07 100

The spice cake was prepared using the following steps:

Dry Mix Procedure:

Place RCS, Mira-Thik 603, Core M90, and sorbitol into mixer bowl. MeltEC-25 in microwave taking care not to get it too hot. (Do not melt GMS90 or Durfax 60). Add EC-25, mix 5 minutes on speed 1, scraping bowl asneeded. Add Durfax 60 while mixing 1 minute on speed 1, scraping bowl asneeded. Add GMS 90 while mixing 1 minute on speed 1, scraping bowl asneeded. Run dry mix through a food processor for 2 minutes, scrapingafter each minute. Transfer dry mix back to mixing bowl. Sift remainingdry ingredients and add slowly (1 large spoonful at a time) to sorbitolmixture while the mixer is running Mix for a total of 5 minutes on speed1.

Water Mixing Procedure:

Place dry mix in bowl. Slowly add water while mixing 30 seconds onspeed 1. Scrape bowl. Mix 3½ minutes on speed 2, scraping bowl asneeded. Spray edges of 8-inch layer cake pan with non-stick spraycooking oil and use a circular parchment paper to line each pan. Pour450 g batter into each cake pan. Bake at 350° F. for 37 minutes or untildone.

Example 36

A cheese sauce comprising an oligosaccharide composition according tothe present invention was prepared.

The ingredients were:

Cheddar 23.41 Butter 5.88 Water 50.50 Sweet Whey 5.44 Disodium phosphate(DSP) 0.73 Trisodium phosphate (TSP) 0.16 Sodium Citrate 0.36 Salt 0.78MaxiGel 420 starch 2.73 RCS (Sample 5) 9.09 Total 100.0

The cheese sauce was prepared using the following steps: Mix allingredients. Heat to 200° F. under constant agitation. Hot fill thecheese sauce into jars or containers and seal with lid or closure. Coolto 40° F.

Example 37

A block of imitation mozzarella cheese comprising an oligosaccharidecomposition according to the present invention was prepared.

The ingredients were:

Weight Percent in g Rennet Casein 19.494 974.70 Sorbic Acid 0.2964 14.82Whey Powder 1.4288 71.44 Soybean Oil 20.121 1006.05 Salt 2.0007 100.04Sodium Citrate 2.09 104.50 Lactic Acid (liquid) 1.2692 63.46 StaSlim 151starch 3.42 171.00 Resistant Corn Syrup 4.75 237.50 (Sample 5, 71% ds)Trisodium phosphate (TSP) 0.76 38.00 Water 44.3699 2218.50 Total 55.63012781.51

The cheese was prepared using the following steps: Add water, sodiumcitrate, casein, and soybean oil (120 g). Blend for five min. Addremaining soybean oil. Add sorbic acid, salt, starch, resistant cornsyrup. Then add whey and lactic acid. Blend for five min. Add remainingingredients. Cook to 185° F.

Example 38

An edible film comprising an oligosaccharide composition according tothe present invention was prepared. Without being bound by theory, it isbelieved that the oligosaccharide composition served as a plasticizer inthe edible film.

The ingredients were:

Solids:

Grams Pullulan (PI-20) 21.252 Star-Dri 1005A 1.65 maltodextrin RCS(Sample 5, 3.3 71% solids) Polysorbate 80 0.165 Na Benzoate 0.033 TOTAL26.4

Film:

Grams Solids 26.4 Water 83.6 TOTAL 110 color/flavor mix 22

The edible film was prepared using the following steps:

Dispersion of Ingredients

Mix pullulan and maltodextrin in a beaker with a whisk. Mix water,polysorbate 80, sodium benzoate, and resistant corn syrup (RCS) in aseparate beaker. Use a Servodyne Mixer Head model 50003-30 to furthermix the wet ingredients. Start with RPM at 700. Slowly add in the dryflavor mix. When all the lumps are gone, slowly add in the pullulanmixture. Adjust the RPM as necessary when the mixture thickens (up to1,000 RPM). When all the dry ingredients are in, stop the mixer andscrape the sides of the beaker. Turn up the mixer to 1,000 RPM and mixfor 2 more minutes. Pour 50 g into centrifuge tubes. Centrifuge for 10minutes to remove air.

Filming Procedure

Films were drawn using a Gardco adjustable drawdown set at 0.045 in.These drawdowns were adjusted to the proper thickness using feeler gaugeblades. Films were drawn onto Mylar with the use of a vacuum plate. Thefilms were dried in an environmental chamber at 65° C. and 25% RH fortwo hours. They were cured in the environmental chamber at 25° C. and28% RH overnight. The dried films were packaged into plastic bags.

Example 39

A low fat pound cake comprising an oligosaccharide composition accordingto the present invention was prepared.

The ingredients were:

Ingredient % Part A Cake flour 28.81 RCS Solids (Sample 5) 26 Water16.27 GMS-90 Emulsifier 5.92 dextrose 4.17 Non-fat dry milk, high heat1.6 STA-SLIM 150 starch 1.29 STA-SLIM 142 starch 0.64 Salt 0.63Leavening acid, Pan-O-Lite 0.5 Baking soda 0.5 Vanilla Flavor #4641740.45 Annatto color 0.1 Xanthan 0.09 Part B Liquid egg whites 8.4 Water4.63 100

The pound cake was prepared using the following steps: Blend dryingredients of Part A in a Hobart mixer at speed 1. Add GMS-90emulsifier and blend for 2 minutes (speed 1). Add water and Annattocolor and blend 4 minutes (speed 2). Scrape bowl and paddle after 2minutes of mixing and at end of mixing. Mix Part B ingredients together.Add in ⅓ of the Part B egg white/water mixture to Part A and blend for 1minute (Speed 2). Scrape bowl and paddle after mixing. Repeat first stepfor Part B twice to incorporate remaining ⅔ of egg white/water mixture.Pour 200 grams of batter into a loaf pan pre-coated with non-stickspray. Bake at 350° F. for 30 minutes.

Example 40

Oatmeal chocolate chip raisin cookies having polyol levels andcomprising an oligosaccharide composition according to the presentinvention were prepared.

The ingredients were:

Formula Baker's Ingredients Percent Percent Vream Rite Shortening 12.5050.40 BAKERY REBALANCE 706 (Tate & Lyle) 9.00 36.29 STA-LITE IIIpolydextrose (Tate & Lyle) 5.00 20.16 Sorbitol (Sorbogem fines) 3.0012.10 NutraFlora ® scFOS ® (Fructo Oligosaccharide) 4.50 18.15 ResistantCorn Syrup (Sample 4) 3.00 12.10 Salt 0.50 2.02 Cinnamon 0.30 1.21Cinnamon flavor 0.25 1.01 Oatmeal cookie flavor 0.25 1.01 Vanilla flavor0.25 1.01 Dry egg 0.90 3.63 Water 9.00 36.29 Glycerine 1.25 5.04 Pastryflour 24.80 100.00 Quick rolled oats 12.40 50.00 Baking soda 0.40 1.61Pan-O-Lite 0.20 0.81 Chopped walnuts 6.00 24.19 Raisins 6.50 26.21 Total100.00 403.23

The oatmeal raisin cookies were prepared using the following steps: Mixshortening and flavors in a N-50 Hobart mixer at speed 1 for 30 seconds.Add the remaining stage 1 ingredients. Mix at speed 1 for 1 min. Scrapethe sides of the bowl. Mix at speed 2 for 1 min. Add the stage 2ingredients. Mix at speed 1 for 1 min. Scrape the sides of the bowl. Mixat speed 2 for 1 min. Add the stage 3 ingredients. Mix at speed 1 for 1min 30 sec. Scrape the sides of the bowl. Repeat mix at speed 1 for 1min 30 sec. Add the stage 4 ingredients. Mix at speed 1 for 15 sec.Weigh 30 g dough piece onto a parchment with double-lined baking pans.Bake 12 cookies in convection oven at 375° F. for 11 min.

Example 41

Soft chocolate cookies comprising an oligosaccharide compositionaccording to the present invention were prepared.

The ingredients were:

Ingredient % Flour, pastry 28.70 Resistant corn syrup solids (Sample 5)22.20 Butter 20.40 RCS (Sample 5, 71% ds) 10.90 Eggs, whole 9.10 Naturalcocoa N-11-N 3.60 Lightly alkalized cocoa D-11-A 2.00 Instant TENDER-JELC food starch modified 1.90 Vanilla flavor 0.46 Salt 0.44 Baking soda0.30 100.00

The cookies were prepared using the following steps: Blend sugar/RCSSolids, butter, and RCS (71% ds) in Hobart mixing bowl on speed 1. Addegg. Dry blend remaining ingredients and add to this mixture. Bake at350° F. for 15 minutes.

Example 42

A maple syrup comprising an oligosaccharide composition according to thepresent invention was prepared.

The ingredients were:

Water 80.132 Resistant Corn Syrup Solids (Sample 5) 17.00 Cellulose Gum1.00 Maple Flavor 0.45 Salt 0.45 SPLENDA sucralose 0.35 Guar Gum 0.28Phosphoric Acid (85%) 0.15 Caramel Color 0.13 Sodium Hexameta Phosphate0.05 Butter Flavor 0.008 Total 100.00

The maple syrup was prepared using the following steps: Add sucralose,preservatives, salt, flavoring, and color to water using slow speed instandard mixer. Slowly add gums to mixture, allowing to hydrate 20-25minutes. Blend in resistant corn syrup solids, while heating to 185° F.Hold for one minute. Remove heat and add acid. Fill containers at180-185° F. and invert for one minute. Cool to 75° F.

Example 43

A barbeque sauce comprising an oligosaccharide composition according tothe present invention was prepared.

The ingredients were:

Part A Tomato Paste 27.23 Water 14.7 Apple Cider Vinegar 15.13 Resistantcorn syrup (Sample 5, 71%) 33.73 Molasses 5.04 Liquid Hickory Smoke 0.30Caramel Color 0.21 Part B Salt 2.02 Spice Blend 1.65 Sucralose 0.014

The barbeque sauce was prepared using the following steps: Heat Part Aingredients on to 190° F. Add dry ingredients to part A and heat for 15minutes at 200° F. Hot fill containers and cool.

Example 44

A French dressing comprising an oligosaccharide composition according tothe present invention was prepared.

The ingredients were:

Soybean oil 9.00 Resistant corn syrup (Sample 5, 71%) 47.57 Vinegar, 120grain 12.00 Water 18.59 Tomato Paste 7.00 Salt 2.00 MiraThik 603 foodstarch modified 2.00 Polysorbate 60 0.20 Onion Powder 0.18 Garlic Powder0.15 Xanthan Gum 0.10 Sorbic Acid 0.10 Oleoresin Paprika 0.10 EDTA 0.01Total 100.0

The French dressing was prepared using the following steps: Place waterand resistant corn syrup in container. Dry mix onion, salt, garlic,sorbic acid, and EDTA and add to water mixture. Slurry starch andxanthan gum in small amount of oil, add to water mixture, and mix forfive minutes to allow starch to hydrate. Add tomato paste and paprika.Add vinegar. Melt polysorbate 60 and add to mixture slowly. Addremaining oil and mix five minutes. Process through a colloid mill at0.26″ (2 revolutions).

Example 45

A cream of chicken soup concentrate comprising an oligosaccharidecomposition according to the present invention was prepared.

The ingredients were:

Water 65.65 Chicken Bouillon 11.30 Resistant Corn Syrup Solids (Sample5) 11.00 Half & half 5.60 Rezista Starch 3.10 Titanium Dioxide 1.00 Salt0.50 Sugar 0.16 Spices 0.69 Xanthan Gum 0.10 Total 100.00

The cream of chicken soup concentrate was prepared using the followingsteps: Mix dry ingredients. Mix liquid ingredients for 3-5 minutes. Adddry ingredients slowly using lightning mixer on medium speed. Mix 3-5minutes ensuring even dispersion. Heat to 190° F. without stirring. Holdfor 5 minutes. Fill hot into cans, seal immediately. Retort at 250° F.for 40 minutes. Cool cans to room temperature. To serve, add one cansoup to equal volume of 2% milk. Mix well. Heat to simmer (approximately10 minutes). Serve hot.

Example 46

A ketchup comprising an oligosaccharide composition according to thepresent invention was prepared.

The ingredients were:

Tomato Paste 37.54 Resistant Corn Syrup Solids (Sample 5) 12.01 Water41.37 Vinegar 120 grain 7.01 Garlic Powder 0.02 Onion Powder 0.03 SmokeFlavor 0.001 Salt 2.00 Sucralose (dry) 0.02

The ketchup was prepared using the following steps: Dry mix spices, RCS,sucralose and salt. Mix water, vinegar, and dry mix using a lighteningmixer. Add smoke flavor to wet mix. Blend tomato paste and ¼ of the wetmix (water, vinegar, and dry mix) in a Hobart mixer with paddleattachment on speed 1 for 2 minutes. Blend in the remainder of the wetmix on speed 1 for 1 minute. Stop and scrape the bowl well. Continueblending on speed 1 for 1 minute. Heat ketchup to 105° C. and hold for15 seconds. Cool to 80° C. Homogenize using Panda homogenizer at 150/50bars. Immediately package in glass jars.

Example 47

A beef-flavored gravy mix comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Water 90.17 Perma-Flo Starch 3.58 Beef Flavors 3.25 Resistant Corn Syrupsolids (Sample 5) 10.00 Sugar 0.43 Sweet Dairy Whey 0.42 Caramel Color0.09 Spices 0.03 Total 100.0

The beef-flavored gravy mix was prepared using the following steps:Blend dry ingredients and TALO TF-55 flavoring (all ingredients exceptwater) until uniformly blended. Using a wire whisk, disperse this drymix into cold water. Cook with agitation to 190° F. Hold mixture at 190°F. with agitation for 10 minutes.

Example 48

A dry blended coffee creamer comprising an oligosaccharide compositionaccording to the present invention was prepared.

The ingredients were:

Commercial creamer powder (Jerzee blend 220077) 21.8 Resistant CornSyrup solids (Sample 5) 78.2

The dry blended coffee creamer was prepared using the following steps:the ingredients are blended, scaled and screened through a 10 meshscreen into a tumble blender vessel, ribbon blender, or paddle blender.The formulation is blended from 10 to 25 minutes and packaged. Silicadioxide or sodium silicoaluminate can be added as anti-caking agents ifrequired.

Example 49

A soy-based dry coffee creamer powder slurry comprising anoligosaccharide composition according to the present invention wasprepared.

The ingredients were:

% Dry pounds solids comp % formula Hydrogenated 65 65 50.67% 23.50%48.64 Soybean oil 105° F. Sodium 4.1 3.895 3.04% 1.48% 3.07 CaseinateResistant corn 61.47 58.4 45.52% 22.23% 46.00 syrup solids (Sample 5)Alphadign 70K 0.5 0.5 0.39% 0.18% 0.37 Mono- and diglycerides BFP 75K0.5 0.5 0.39% 0.18% 0.37 mono- and diglycerides water 145 0 0.00% 52.43%108.50 276.57 128.3 100.00% 100.00% 206.95 Total solids 46.39% Yield @4% 100.00 moisture

The water is added to a batch tank and is heated to 120 to 140° F. Thesodium caseinate is added to the water and allowed to hydrate for 10 to30 minutes. The mono and diglycerides can be melted into thehydrogenated soybean oil or melted separately. Once the sodium caseinatehas been hydrated the soybean oil and mono and diglycerides are added tothe batch tank. The mixture is well blended. The remaining resistantcorn syrup is added to the batch tank and the mixture is heated to 170°F., homogenized via double stage homogenization (if required) and heldfor 30 minutes. The product is then ready to be spray dried with a inlettemperature of 350 to 500° F. and an exhaust temperature of 150 to 200°F. An optional fluid bed dryer can be used. Sodium silicoaluminate orsilica dioxide could also be included for anti-caking purposes.Phosphate salts and/or anti-caking agents could also be included.

Example 50

A coconut-based coffee creamer powder slurry for spray-drying,comprising an oligosaccharide composition according to the presentinvention was prepared.

The ingredients were:

Ingredients pounds solids % dry comp % form Hydrogenated Coconut Oil 3232 48.51% 21.67% 46.57 92 Sodium Caseinate 3.2 3.04 4.61% 2.17% 4.66Resistant corn syrup solids 31 29.45 44.65% 20.99% 45.12 (Sample 5)Dipotassium Phosphate 0.4 0.392 0.59% 0.27% 0.58 Distilled mono- and1.08 1.08 1.64% 0.73% 1.57 diglycerides water 80 0 0.00% 54.17% 116.43147.68 65.96 100.00% 100.00% 214.93 Total solids 44.67% Yield @ 4%100.00 moisture

A coconut-based coffee creamer powder was prepared using the followingsteps: The water is added to a batch tank and is heated to 120 to 140°F. The sodium caseinate is added to the water and allowed to hydrate for10 to 30 minutes. The mono and diglycerides can be melted into thehydrogenated coconut oil or melted separately. Once the sodium caseinatehas been hydrated, the coconut oil and mono and diglycerides are addedto the batch tank. The mixture is well blended. The remainingingredients resistant corn syrup and dipotassium phosphate are added tothe batch tank and the mixture is heated to 170° F., homogenized viadouble stage homogenization (if required), and held for 30 minutes. Theproduct is then ready to be spray dried with a inlet temperature of 350to 500° F. and an exhaust temperature of 150 to 200° F. An optionalfluid bed dryer can be used. Sodium silicoaluminate or silica dioxidecould also be included for anti-caking purposes.

Example 51

An ice cream coating and/or compound coating can be prepared usingresistant corn syrup solids to lower or eliminate sugar content therebyreducing overall calories. Fiber content can be significantly enhancedin comparison to a typical coating, (e.g., this illustration has 33grams/100 grams versus a comparable control at 5 gram/100 grams ofcoating).

Ingredients percentage Resistant corn syrup solids (sample 5) 40.5Vegetable Shortening (92 coconut) 45.0 Cocoa powder 10/12 (fat) 14.0Lecithin 0.45 sucralose 0.05 total 100.00

The ice cream coating and/or compound coating can be prepared using thefollowing steps: Grind corn syrup solids to a particle size between5-125 microns, average near 30-40 micron. Sieve solids to achievedesired particles. Combine cocoa powder and sucralose with corn syrupsolids. Melt shortening and combine with lecithin. While mixing theblended dry ingredients, add the melted shortening/lecithin combination,scraping the bowl regularly. Apply to frozen novelties, baked goods,etc. as desired.

Example 52

Two samples of resistant corn syrup (RCS) were prepared as in Sample 5of Example 16 above, one of which had a lower monosaccharide content.(“LS” in the following description refers to “low sugar.”) The wt %d.s.b. of monosaccharides, disaccharides, trisaccharides, and tetra- andhigher order saccharides were as follows:

Formulation DP1 DP2 DP3 DP4+ RCS 12.5 4.7 4.1 78.7 RCS LS 1.6 4.6 4.689.2

Samples of the two resistant corn syrups and maltodextrin were fed todogs. Blood samples were taken from the dogs at intervals after thefeeding to determine the glycemic response. The changes in blood glucoseconcentrations over time are shown in FIG. 15, and are summarized in thetable below.

Item Maltodextrin RCS RCS LS SEM N 5 5 5 Time to glucose peak, min 30 1818 4.9 Incremental area under the 155.1^(d) 37.7^(b) 73.9^(c) 12.9 curvefor glucose Relative glycemic response 100.0^(d) 24.5^(b) 50.1^(c) 7.8^(ab)Means in the same row with different superscripts are different (P< 0.05). SEM = standard error of the mean.

Example 53

Six samples of resistant corn syrup were prepared as in Sample 5 ofExample 16 above. Each sample was a 72% ds syrup, with the balance beingwater. The samples contained essentially no fat, protein, or ash. Thesix samples were:

RCS GR1 (RCS, 72% ds syrup 70% fiber, 15% sugar) (“sugar” in thesesamples refers to the total of mono- and disaccharides)

RCS GR2 (RCS LS, 72% ds syrup 80% fiber, 5% sugar)

RCS GR3 (RCS with 50% fructose, 72% ds syrup)

RCS GR4 (RCS with 50% sorbitol, 72% ds syrup)

RCS GR5 (RCS LS with 25% fructose, 72% ds syrup)

RCS GR6 (RCS LS, with 25% sorbitol, 72% ds syrup)

Samples containing 25 g (dsb) of the syrup were prepared as follows.2.838 kg of filtered water was added to a jug containing a pre-weighedquantity of RCS. The lid was placed on the jug, and it was then mixedthoroughly by shaking and swirling until all syrup was dissolved. 12 oz.(350 g) of this solution contained 25 g of the test carbohydrate on adry solids basis.

The control solution was prepared by mixing 25 g anhydrous glucose with300 mL of water.

The samples were administered to 10 healthy human subjects. Thecharacteristics of the subjects were: 5 male, 5 female; age, 35±10 y;body mass index, 24.0±3.8 kg/m′. Each subject undertook nine tests onseparate days which included the six test foods and on three occasionsthe standard glucose drink containing 25 g of available carbohydrate.Blood glucose was measured fasting and at 15, 30, 45, 60, 90 and 120minutes after eating. Incremental areas under the blood glucose responsecurves (iAUC) were calculated. Each subject's iAUC after consumption ofeach test food was expressed as a percentage of the mean iAUC of thethree glucose controls taken by the same subject. The incremental areasunder the curve and relative glycemic response (RGR) of the productswere:

iAUC RGR Glucose (25 g) 124.4 ± 13.5^(a) 100^(a) RCS GR1 38.5 ± 4.6^(b)32.6 ± 3.8^(b) RCS GR2 25.6 ± 3.7^(b) 23.2 ± 4.6^(b) RCS GR3 30.1 ±4.4^(b) 26.2 ± 4.2^(b) RCS GR4 17.4 ± 4.1^(b) 15.3 ± 3.6^(c) RCS GR527.6 ± 4.0^(b) 25.4 ± 4.3^(b) RCS GR6 20.9 ± 4.0^(b) 18.2 ± 3.5^(c)

Values with different superscripts differ significantly (p<0.001). Therewere no statistically significant differences in palatability ratingsbetween any of the foods.

Example 54

Sweetose® 4300 corn syrup (81% ds) was evaporated to less than 6%moisture content by passing it through a hot oil jacketed paddle mixerat a rate of 77 kg/h. The paddle mixer rotor speed was typically set for300 to 600 rpm and the oil jacket temperature was varied from 150° C. to205° C. In some of the tests phosphoric acid was added at a rate to givefrom 0.1% to 0.4% phosphoric acid solids on corn syrup solids. In someof the tests hydrochloric acid was added at 25 ppm, in place of or inaddition to the phosphoric acid.

Product collected from these tests (25 mg) was dissolved in 4 mL of pH4.0 buffer and incubated with 100 microliters of a 10 mg/mLamyloglucosidasc enzyme (Amyloglucoxidase Sigma Catalog #A-7255)solution for 2 hours at 45° C. An aliquot from this incubation wastreated with a small quantity of ion exchange resin and filtered (0.45microns) prior to saccharide distribution analysis by liquidchromatography. From this analysis, the weight percent of carbohydratefound to exist as trisaccharides and higher was quantified as digestionresistant carbohydrate and is labeled as % fiber in the table below:

Sample name Temp ° C. % H₃PO₄ HCl ppm % fiber run 1 194 0.2% 43 run 2195 0.2% 25 52 run 3 193 0.4% 25 62 run 4 203 0.4% 25 68 run 5 180 0.2%27 run 6 181 0.4% 37 run 7 181 0.4% 25 33 polydextrose control 82

A laboratory sample of polydextrose was used as a control for this test,and showed a level of approximately 82% fiber.

Example 55

Sweetose® 4300 corn syrup (81% ds) was evaporated to less than 3%moisture content by passing it through a hot oil jacketed paddle mixerat a rate of 77 kg/h. The paddle mixer rotor speed was typically set for800 rpm and the oil jacket temperature was set to 210° C. In some of thetests phosphoric acid was added at a rate to give from 0.1% to 0.4%phosphoric acid solids on corn syrup solids. In some of the testshydrochloric acid was added at 25 or 50 ppm, in place of or in additionto the phosphoric acid.

Product collected from these tests (25 mg) was dissolved in 4 mL of pH4.0 buffer and incubated with 100 microliters of a 10 mg/mLamyloglucosidase enzyme (Amyloglucoxidase Sigma Catalog #A-7255)solution for 2 hours at 45° C. An aliquot from this incubation wastreated with a small quantity of ion exchange resin and filtered (0.45microns) prior to saccharide distribution analysis by liquidchromatography. From this analysis, the weight percent of carbohydratefound to exist as trisaccharides and higher was quantified as digestionresistant carbohydrate and is labeled as % fiber in the table below:

Sample name Temp ° C. % H₃PO₄ HCl ppm % fiber run 2-1 210 0.0% 11 run2-2 210 0.2% 79 run 2-3 210 0.0% 12 run 2-4 210 0.1% 43 run 2-5 210 0.1%51 run 2-6 210 0.2% 61 run 2-7 210 0.3% 84 run 2-8 210 0.2% 25 79 run2-9 210 0.0% 11 run 2-10 210 0.1% 43 run 2-11 210 0.1% 25 57 run 2-12210 0.2% 53 run 2-13 210 0.2% 25 62 run 2-14 210 0.4% 56 run 2-15 2100.4% 25 55 run 2-16 210 0.4% 50 62 run 2-17 210 0.0% 50 65 run 2-18 2100.0% 50 59 polydextrose control 82

A laboratory sample of polydextrose was used as a control for this test,and showed a level of approximately 82% fiber.

Example 56

500 grams of Staley 300 corn syrup (80.0% ds, 35 DE, 0% fiber, 4 kcal/g)was thoroughly blended with 500 grams of resistant corn syrup (69.0% ds,21 DE, 71% fiber, 2 kcal/g) to give 1 kg of corn syrup fiber (74.5% ds,28 DE, 35% fiber, 3 kcal/g).

Example 57

500 grams of Staley 1300 corn syrup (80.3% ds, 43 DE, 0% fiber, 4kcal/g) was thoroughly blended with 500 grams of resistant corn syrup(69.0% ds, 21 DE, 71% fiber, 2 kcal/g) to give 1 kg of corn syrup fiber(74.7% ds, 32 DE, 35% fiber, 3 kcal/g).

Example 58

500 grams of Staley 4300 corn syrup (81.6% ds, 63 DE, 0% fiber, 4kcal/g) was thoroughly blended with 500 grams of resistant corn syrup(69.0% ds, 21 DE, 71% fiber, 2 kcal/g) to give 1 kg of corn syrup fiber(75.3% ds, 42 DE, 35% fiber, 3 kcal/g).

Example 59

500 grams of Staleydex 130 syrup (70.5% d s, 99 DE, 0% fiber, 4 kcal/g)was thoroughly blended with 500 grams of resistant corn syrup (69.0% ds,21 DE, 71% fiber, 2 kcal/g) to give 1 kg of corn syrup fiber (69.8% ds,60 DE, 35% fiber, 3 kcal/g).

The preceding description of specific embodiments of the invention isnot intended to be a list of every possible embodiment of the invention.Persons skilled in the art will recognize that other embodiments wouldbe within the scope of the following claims. For example, certainspecific slowly digestible or digestion resistant compositions are usedas ingredients in food products in some of the above examples. It shouldbe recognized that other slowly digestible or digestion resistantcompositions of the present invention could be used instead in thosesame food products, although the exact characteristics of the foodproduct may vary to some degree depending on the exact nature of theingredients used. Many other modifications could also be made to thespecific examples herein.

1. A process for making a slowly-digestible or digestion-resistantcarbohydrate composition, the process comprising providing an aqueousfeed composition that comprises dextrose and at least one lineardextrose oligomer, the aqueous feed composition including at least 70%by weight on a dry solids basis of dextrose and dextrose oligomers, theaqueous feed composition having a dextrose equivalence of 26-95; andreacting the aqueous feed composition at a total solids concentration ofat least about 90% by weight in the presence of at least one acidcatalyst that accelerates the rate of cleavage or formation of glucosylbonds at a pH of no more than 4 and a temperature of at least about 149°C. for a time of 0.1-15 minutes to produce a product composition inwhich the concentration of non-linear saccharide oligomers is at leasttwice as high as the concentration of linear saccharide oligomers, andin which the concentration of non-linear saccharide oligomers having adegree of polymerization of at least three is at least about 50% byweight on a dry solids basis, the product composition being primarilydigestion resistant or primarily slowly digestible as measured by theEnglyst Assay, the product composition including less than 50% on a drysolids basis of residual monosaccharides, wherein the dextrose oligomersand the saccharide oligomers have a degree of polymerization of 2 to 30,and wherein the slowly-digestible or digestion-resistant carbohydratecomposition is not a polydextrose.
 2. The process of claim 1, whereinthe aqueous feed composition consists essentially of a starchhydrolyzate.
 3. The process of claim 1, wherein the reacting of theaqueous feed composition in the presence of the at least one acidcatalyst is performed at a pH of about 1.0 to about 2.5.
 4. The processaccording to claim 1, wherein the reacting of the aqueous feedcomposition in the presence of the at least one acid catalyst isperformed in a continuous flow through a reactor or a pipe.
 5. Theprocess according to claim 1, wherein the product composition comprisesa minor amount of residual monosaccharide, and wherein the processfurther comprises removing at least some residual monosaccharide fromthe product composition by fractionation.
 6. The process according toclaim 1, wherein the process does not include removing residualmonosaccharide from the product composition by fractionation.
 7. Theprocess according to claim 1, wherein the process does not include ahydrogenation step.
 8. The process according to claim 1, wherein theproduct composition is primarily digestion resistant as measured by theEnglyst Assay
 9. The process of claim 1, wherein the aqueous feedcomposition consists essentially of a starch hydrolyzate, and thecatalyst is hydrochloric acid, sulfuric acid, phosphoric acid, or acombination thereof, and the reacting of the aqueous feed composition inthe presence of the at least one acid catalyst is performed at a pH ofabout 1.0 to about 2.5.
 10. A food product comprising a food compositionand a primarily slowly-digestible or primarily digestion-resistantcarbohydrate composition in which the concentration of non-linearsaccharide oligomers is at least twice as high as the concentration oflinear saccharide oligomers, and in which the concentration ofnon-linear saccharide oligomers having a degree of polymerization of atleast three is at least about 50% by weight on a dry solids basis, thecomposition including less than 50% on a dry solids basis of residualmonosaccharides, the composition being primarily slowly-digestible orprimarily digestion-resistant as measured by the Englyst Assay, thecarbohydrate composition being made by a process according to claim 1,wherein the food product is selected from baked foods, breakfast cereal,anhydrous coatings, dairy products, confections, jams and jellies,beverages, fillings, extruded and sheeted snacks, gelatin desserts,snack bars, cheese and cheese sauces, edible and water-soluble films,soups, syrups, sauces, dressings, creamers, icings, frostings, glazes,pet food, tortillas, meat and fish, dried fruit, infant and toddlerfood, and batters and breadings.
 11. A process for making aslowly-digestible or digestion-resistant carbohydrate composition, theprocess comprising providing an aqueous feed composition that consistsessentially of water and saccharides consisting essentially of dextroseand one or more linear dextrose oligomers; and reacting the aqueous feedcomposition at a total solids concentration of at least about 90% byweight in the presence of at least one acid catalyst that acceleratesthe rate of cleavage or formation of glucosyl bonds at a pH of no morethan 4 and a temperature of at least about 149° C. for a time of 0.1-15minutes to produce a product composition in which the concentration ofnon-linear saccharide oligomers is at least twice as high as theconcentration of linear saccharide oligomers, and in which theconcentration of non-linear saccharide oligomers having a degree ofpolymerization of at least three is at least about 50% by weight on adry solids basis, the product composition being primarily digestionresistant or primarily slowly digestible as measured by the EnglystAssay, the product composition including less than 50% on a dry solidsbasis of residual monosaccharides, wherein the dextrose oligomers andthe saccharide oligomers have a degree of polymerization of 2 to
 30. 12.The process of claim 11, wherein the aqueous feed composition consistsessentially of a starch hydrolyzate.
 13. The process of claim 11,wherein the catalyst is hydrochloric acid, sulfuric acid, phosphoricacid, or a combination thereof.
 14. The process of claim 11, wherein thereacting of the aqueous feed composition in the presence of the at leastone acid catalyst is performed at a pH of about 1.0 to about 2.5. 15.The process according to claim 11, wherein the reacting of the aqueousfeed composition in the presence of the at least one acid catalyst isperformed in a continuous flow through a reactor or a pipe.
 16. Theprocess according to claim 11, wherein the product composition comprisesa minor amount of residual monosaccharide, and wherein the processfurther comprises removing at least some residual monosaccharide fromthe product composition by fractionation.
 17. The process according toclaim 11, wherein the process does not include removing residualmonosaccharide from the product composition by fractionation.
 18. Theprocess according to claim 11, wherein the process does not include ahydrogenation step.
 19. The process of claim 11, wherein the catalyst ishydrochloric acid, sulfuric acid, phosphoric acid, or a combinationthereof, and wherein the reacting of the aqueous feed composition in thepresence of the at least one acid catalyst is performed at a pH of about1.0 to about 2.5.
 20. A food product comprising a food composition and aprimarily slowly-digestible or primarily digestion-resistantcarbohydrate composition in which the concentration of non-linearsaccharide oligomers is at least twice as high as the concentration oflinear saccharide oligomers, and in which the concentration ofnon-linear saccharide oligomers having a degree of polymerization of atleast three is at least about 50% by weight on a dry solids basis, thecomposition including less than 50% on a dry solids basis of residualmonosaccharides, the composition being primarily slowly-digestible orprimarily digestion-resistant as measured by the Englyst Assay, thecarbohydrate composition being made by a process according to claim 1,wherein the food product is selected from baked foods, breakfast cereal,anhydrous coatings, dairy products, confections, jams and jellies,beverages, fillings, extruded and sheeted snacks, gelatin desserts,snack bars, cheese and cheese sauces, edible and water-soluble films,soups, syrups, sauces, dressings, creamers, icings, frostings, glazes,pet food, tortillas, meat and fish, dried fruit, infant and toddlerfood, and batters and breadings.